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CN104516218B - Electrophotographic photoreceptor, method for producing the same, and image forming apparatus and method - Google Patents

Electrophotographic photoreceptor, method for producing the same, and image forming apparatus and method Download PDF

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Publication number
CN104516218B
CN104516218B CN201410513484.XA CN201410513484A CN104516218B CN 104516218 B CN104516218 B CN 104516218B CN 201410513484 A CN201410513484 A CN 201410513484A CN 104516218 B CN104516218 B CN 104516218B
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China
Prior art keywords
fine particles
electrophotographic photoreceptor
photoreceptor
image
layer
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CN201410513484.XA
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CN104516218A (en
Inventor
波多野北斗
栗本和典
前田诚亮
高尾弘毅
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Konica Minolta Inc
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Konica Minolta Inc
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Priority claimed from JP2013209063A external-priority patent/JP5900451B2/en
Priority claimed from JP2013255808A external-priority patent/JP5915633B2/en
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Publication of CN104516218A publication Critical patent/CN104516218A/en
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    • G—PHYSICS
    • G03—PHOTOGRAPHY; CINEMATOGRAPHY; ANALOGOUS TECHNIQUES USING WAVES OTHER THAN OPTICAL WAVES; ELECTROGRAPHY; HOLOGRAPHY
    • G03G—ELECTROGRAPHY; ELECTROPHOTOGRAPHY; MAGNETOGRAPHY
    • G03G5/00—Recording members for original recording by exposure, e.g. to light, to heat, to electrons; Manufacture thereof; Selection of materials therefor
    • G03G5/02—Charge-receiving layers
    • G03G5/04—Photoconductive layers; Charge-generation layers or charge-transporting layers; Additives therefor; Binders therefor
    • G03G5/05—Organic bonding materials; Methods for coating a substrate with a photoconductive layer; Inert supplements for use in photoconductive layers
    • G03G5/0528—Macromolecular bonding materials
    • G03G5/0557—Macromolecular bonding materials obtained otherwise than by reactions only involving carbon-to-carbon unsatured bonds
    • G03G5/0575—Other polycondensates comprising nitrogen atoms with or without oxygen atoms in the main chain
    • G—PHYSICS
    • G03—PHOTOGRAPHY; CINEMATOGRAPHY; ANALOGOUS TECHNIQUES USING WAVES OTHER THAN OPTICAL WAVES; ELECTROGRAPHY; HOLOGRAPHY
    • G03G—ELECTROGRAPHY; ELECTROPHOTOGRAPHY; MAGNETOGRAPHY
    • G03G5/00—Recording members for original recording by exposure, e.g. to light, to heat, to electrons; Manufacture thereof; Selection of materials therefor
    • G03G5/02—Charge-receiving layers
    • G03G5/04—Photoconductive layers; Charge-generation layers or charge-transporting layers; Additives therefor; Binders therefor
    • G03G5/05—Organic bonding materials; Methods for coating a substrate with a photoconductive layer; Inert supplements for use in photoconductive layers
    • G03G5/0503—Inert supplements
    • G03G5/0507—Inorganic compounds
    • G—PHYSICS
    • G03—PHOTOGRAPHY; CINEMATOGRAPHY; ANALOGOUS TECHNIQUES USING WAVES OTHER THAN OPTICAL WAVES; ELECTROGRAPHY; HOLOGRAPHY
    • G03G—ELECTROGRAPHY; ELECTROPHOTOGRAPHY; MAGNETOGRAPHY
    • G03G5/00—Recording members for original recording by exposure, e.g. to light, to heat, to electrons; Manufacture thereof; Selection of materials therefor
    • G03G5/02—Charge-receiving layers
    • G03G5/04—Photoconductive layers; Charge-generation layers or charge-transporting layers; Additives therefor; Binders therefor
    • G03G5/05—Organic bonding materials; Methods for coating a substrate with a photoconductive layer; Inert supplements for use in photoconductive layers
    • G03G5/0528—Macromolecular bonding materials
    • G03G5/0532—Macromolecular bonding materials obtained by reactions only involving carbon-to-carbon unsatured bonds
    • G03G5/0542—Polyvinylalcohol, polyallylalcohol; Derivatives thereof, e.g. polyvinylesters, polyvinylethers, polyvinylamines
    • G—PHYSICS
    • G03—PHOTOGRAPHY; CINEMATOGRAPHY; ANALOGOUS TECHNIQUES USING WAVES OTHER THAN OPTICAL WAVES; ELECTROGRAPHY; HOLOGRAPHY
    • G03G—ELECTROGRAPHY; ELECTROPHOTOGRAPHY; MAGNETOGRAPHY
    • G03G5/00—Recording members for original recording by exposure, e.g. to light, to heat, to electrons; Manufacture thereof; Selection of materials therefor
    • G03G5/02—Charge-receiving layers
    • G03G5/04—Photoconductive layers; Charge-generation layers or charge-transporting layers; Additives therefor; Binders therefor
    • G03G5/05—Organic bonding materials; Methods for coating a substrate with a photoconductive layer; Inert supplements for use in photoconductive layers
    • G03G5/0528—Macromolecular bonding materials
    • G03G5/0532—Macromolecular bonding materials obtained by reactions only involving carbon-to-carbon unsatured bonds
    • G03G5/0546—Polymers comprising at least one carboxyl radical, e.g. polyacrylic acid, polycrotonic acid, polymaleic acid; Derivatives thereof, e.g. their esters, salts, anhydrides, nitriles, amides
    • G—PHYSICS
    • G03—PHOTOGRAPHY; CINEMATOGRAPHY; ANALOGOUS TECHNIQUES USING WAVES OTHER THAN OPTICAL WAVES; ELECTROGRAPHY; HOLOGRAPHY
    • G03G—ELECTROGRAPHY; ELECTROPHOTOGRAPHY; MAGNETOGRAPHY
    • G03G5/00—Recording members for original recording by exposure, e.g. to light, to heat, to electrons; Manufacture thereof; Selection of materials therefor
    • G03G5/02—Charge-receiving layers
    • G03G5/04—Photoconductive layers; Charge-generation layers or charge-transporting layers; Additives therefor; Binders therefor
    • G03G5/05—Organic bonding materials; Methods for coating a substrate with a photoconductive layer; Inert supplements for use in photoconductive layers
    • G03G5/0528—Macromolecular bonding materials
    • G03G5/0592—Macromolecular compounds characterised by their structure or by their chemical properties, e.g. block polymers, reticulated polymers, molecular weight, acidity
    • G—PHYSICS
    • G03—PHOTOGRAPHY; CINEMATOGRAPHY; ANALOGOUS TECHNIQUES USING WAVES OTHER THAN OPTICAL WAVES; ELECTROGRAPHY; HOLOGRAPHY
    • G03G—ELECTROGRAPHY; ELECTROPHOTOGRAPHY; MAGNETOGRAPHY
    • G03G5/00—Recording members for original recording by exposure, e.g. to light, to heat, to electrons; Manufacture thereof; Selection of materials therefor
    • G03G5/14—Inert intermediate or cover layers for charge-receiving layers
    • G03G5/147—Cover layers
    • G03G5/14704—Cover layers comprising inorganic material
    • G—PHYSICS
    • G03—PHOTOGRAPHY; CINEMATOGRAPHY; ANALOGOUS TECHNIQUES USING WAVES OTHER THAN OPTICAL WAVES; ELECTROGRAPHY; HOLOGRAPHY
    • G03G—ELECTROGRAPHY; ELECTROPHOTOGRAPHY; MAGNETOGRAPHY
    • G03G5/00—Recording members for original recording by exposure, e.g. to light, to heat, to electrons; Manufacture thereof; Selection of materials therefor
    • G03G5/14—Inert intermediate or cover layers for charge-receiving layers
    • G03G5/147—Cover layers
    • G03G5/14708—Cover layers comprising organic material
    • G—PHYSICS
    • G03—PHOTOGRAPHY; CINEMATOGRAPHY; ANALOGOUS TECHNIQUES USING WAVES OTHER THAN OPTICAL WAVES; ELECTROGRAPHY; HOLOGRAPHY
    • G03G—ELECTROGRAPHY; ELECTROPHOTOGRAPHY; MAGNETOGRAPHY
    • G03G5/00—Recording members for original recording by exposure, e.g. to light, to heat, to electrons; Manufacture thereof; Selection of materials therefor
    • G03G5/14—Inert intermediate or cover layers for charge-receiving layers
    • G03G5/147—Cover layers
    • G03G5/14708—Cover layers comprising organic material
    • G03G5/14713—Macromolecular material
    • G03G5/14717—Macromolecular material obtained by reactions only involving carbon-to-carbon unsaturated bonds
    • G03G5/14734—Polymers comprising at least one carboxyl radical, e.g. polyacrylic acid, polycrotonic acid, polymaleic acid; Derivatives thereof, e.g. their esters, salts, anhydrides, nitriles, amides
    • G—PHYSICS
    • G03—PHOTOGRAPHY; CINEMATOGRAPHY; ANALOGOUS TECHNIQUES USING WAVES OTHER THAN OPTICAL WAVES; ELECTROGRAPHY; HOLOGRAPHY
    • G03G—ELECTROGRAPHY; ELECTROPHOTOGRAPHY; MAGNETOGRAPHY
    • G03G5/00—Recording members for original recording by exposure, e.g. to light, to heat, to electrons; Manufacture thereof; Selection of materials therefor
    • G03G5/14—Inert intermediate or cover layers for charge-receiving layers
    • G03G5/147—Cover layers
    • G03G5/14708—Cover layers comprising organic material
    • G03G5/14713—Macromolecular material
    • G03G5/14747—Macromolecular material obtained otherwise than by reactions only involving carbon-to-carbon unsaturated bonds
    • G03G5/14769—Other polycondensates comprising nitrogen atoms with or without oxygen atoms in the main chain
    • G—PHYSICS
    • G03—PHOTOGRAPHY; CINEMATOGRAPHY; ANALOGOUS TECHNIQUES USING WAVES OTHER THAN OPTICAL WAVES; ELECTROGRAPHY; HOLOGRAPHY
    • G03G—ELECTROGRAPHY; ELECTROPHOTOGRAPHY; MAGNETOGRAPHY
    • G03G5/00—Recording members for original recording by exposure, e.g. to light, to heat, to electrons; Manufacture thereof; Selection of materials therefor
    • G03G5/14—Inert intermediate or cover layers for charge-receiving layers
    • G03G5/147—Cover layers
    • G03G5/14708—Cover layers comprising organic material
    • G03G5/14713—Macromolecular material
    • G03G5/14791—Macromolecular compounds characterised by their structure, e.g. block polymers, reticulated polymers, or by their chemical properties, e.g. by molecular weight or acidity

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  • Physics & Mathematics (AREA)
  • General Physics & Mathematics (AREA)
  • Spectroscopy & Molecular Physics (AREA)
  • Chemical & Material Sciences (AREA)
  • Chemical Kinetics & Catalysis (AREA)
  • Inorganic Chemistry (AREA)
  • Photoreceptors In Electrophotography (AREA)

Abstract

The invention relates to an electrophotographic photoreceptor, an image forming apparatus and an image forming method, which have good cleaning performance and can inhibit the density unevenness of the formed image. The electrophotographic photoreceptor is formed by forming a photosensitive layer on a conductive support and forming a surface layer on the photosensitive layer, wherein the surface layer is formed by containing organic resin fine particles and metal oxide fine particles in a cured resin obtained by polymerizing a compound having two or more radical polymerizable functional groups, and the organic resin fine particles are fine particles which are composed of a resin containing a constituent unit derived from at least one of melamine and benzoguanamine and have a number-average primary particle diameter of 0.01 to 3.00 [ mu ] m.

Description

Electrophotographic photoreceptor, method for producing the same, and image forming apparatus and method
Technical Field
The present invention relates to an electrophotographic photoreceptor provided in an electrophotographic image forming apparatus, a method for manufacturing the electrophotographic photoreceptor, an image forming apparatus provided with the electrophotographic photoreceptor, and an image forming method using the electrophotographic photoreceptor.
Background
Conventionally, as electrophotographic photoreceptors (hereinafter, also simply referred to as "photoreceptors") used in electrophotographic image forming apparatuses, inorganic photoreceptors and organic photoreceptors have been known. The "electrophotographic system" as referred to herein is generally an image forming process in which a photoconductive photoreceptor is first charged by corona discharge in a dark place, then exposed to light, only the charge of the exposed portion is selectively dissipated to obtain an electrostatic latent image, and the latent image portion is developed and visualized with toner made of a coloring agent such as a dye or a pigment, a resin material, or the like to form an image.
Organic photoreceptors have advantages over inorganic photoreceptors in terms of flexibility in the photosensitive wavelength range, film-forming properties, flexibility, transparency of the film, mass productivity, toxicity, cost, and the like, and therefore organic photoreceptors are used in most of the photoreceptors at present.
In recent years, by providing a surface layer made of a crosslinked cured resin to the surface of an organic photoreceptor, abrasion resistance, scratch resistance, and environmental stability can be improved, and the service life can be extended.
Such a surface layer has a relatively smooth surface, has a relatively small surface roughness as compared with a surface layer not composed of a crosslinking-type cured resin, and is difficult to thicken. Therefore, the contact area with the cleaning blade becomes large, the torque increases, and a severe stick-slip (stick-slip) vibration is caused, which causes a problem that poor cleaning is likely to occur. In order to solve this problem, as disclosed in, for example, patent document 1 (jp 2003-a 149995) and patent document 2 (jp 2007-a 94240), a lubricant is supplied to the surface of the photoreceptor to reduce the adhesion between the photoreceptor and the toner and the adhesion between the photoreceptor and the cleaning blade.
However, in the method of adding a lubricant to a developer and supplying the lubricant to the surface of a photoreceptor by a developing bias in a developing step as in patent document 2, for example, a sufficient amount of the lubricant may not be supplied to the surface of the photoreceptor, and the above adhesion force may not be sufficiently reduced, thereby failing to obtain good cleanability. In addition, even in the case of the roller charging method, the charging method performed in the charging step has a problem that discharge products are likely to adhere to the surface of the photoreceptor, and the above-mentioned adhesion force cannot be sufficiently reduced, and thus good cleaning performance cannot be obtained. On the other hand, although the cleaning performance is improved by increasing the amount of lubricant supplied, the uneven supply of lubricant due to the difference in image printing rate is likely to occur, and thus there is a problem that an image density difference occurs between a position where the amount of lubricant adhered is large and a position where the amount of lubricant adhered is small.
On the other hand, it is known that metal oxide fine particles are added to a surface layer of a photoreceptor in order to obtain a photoreceptor having high durability. In particular, by using metal oxide fine particles having a low resistance and a large particle diameter (particularly 100nm or more), both high durability and potential stability can be achieved.
On the other hand, it is known to add an organic filler to the surface layer of the photoreceptor in order to improve the cleaning property. By adding the organic filler, the surface of the photoreceptor is appropriately roughened, and thus the cleaning property can be improved.
Patent document 3 (jp-a-5-224453) discloses adding a benzoguanamine-melamine-formaldehyde condensate to the surface layer of a photoreceptor. Further, patent document 4 (jp-a-5-181299) discloses that fine benzoguanamine resin particles and fine melamine resin particles are added to the surface layer of a photoreceptor.
Such an organic filler such as a benzoguanamine-melamine-formaldehyde condensate has a small adhesion to a toner, and therefore, the effect of improving the cleaning property is particularly high. However, when such an organic filler is used together with the metal oxide fine particles, aggregation occurs in the coating liquid for forming the surface layer. In particular, when used together with metal oxide fine particles having a large particle diameter, aggregation is likely to occur. Aggregates in the coating liquid remain in the formed photoreceptor, and the desired effect cannot be expected. In addition, since the aggregate exists in the surface layer, abnormal abrasion of the cleaning blade occurs, and the cleaning performance is remarkably reduced.
Patent document 1: japanese patent laid-open No. 2003-149995
Patent document 2: japanese patent laid-open publication No. 2007-94240
Patent document 3: japanese laid-open patent publication No. 5-224453
Patent document 4: japanese laid-open patent publication No. 5-181299
Disclosure of Invention
The present invention has been made in view of the above circumstances, and an object thereof is to provide an electrophotographic photoreceptor, an image forming apparatus, and an image forming method, which have good cleaning properties and can suppress density unevenness of a formed image. Further, an electrophotographic photoreceptor having good cleaning properties and high durability and a method for producing the same are provided. Another object of the present invention is to provide an image forming apparatus capable of forming a high-quality image for a long period of time.
The electrophotographic photoreceptor is characterized in that the surface layer is formed by containing organic resin fine particles and metal oxide fine particles in a cured resin obtained by polymerizing a compound having two or more radical polymerizable functional groups, the organic resin fine particles are organic resin fine particles having a uniform number of primary particle diameters of 0.01 to 3.00 [ mu ] m and composed of a resin containing a constituent unit derived from at least one of melamine and benzoguanamine.
In the electrophotographic photoreceptor of the present invention, the organic resin fine particles are preferably a polycondensate of melamine and formaldehyde.
In the electrophotographic photoreceptor of the present invention, the organic resin fine particles are preferably contained in a proportion of 5 to 40 parts by mass with respect to 100 parts by mass of the cured resin.
In the electrophotographic photoreceptor of the present invention, the metal oxide fine particles are preferably surface-treated with a surface treatment agent comprising a compound having a radical polymerizable functional group.
In the electrophotographic photoreceptor of the present invention, the curable resin is preferably an acrylic resin.
In the electrophotographic photoreceptor of the present invention, the surface layer preferably contains a charge transporting compound.
An image forming apparatus according to the present invention includes: an electrophotographic photoreceptor; a charging mechanism for charging the surface of the electrophotographic photoreceptor; an exposure mechanism for forming an electrostatic latent image on the surface of the electrophotographic photoreceptor; a developing mechanism for developing the electrostatic latent image with a developer containing a toner to form a toner image; a transfer mechanism for transferring the toner image to a transfer material; a fixing mechanism for fixing the toner image transferred to the transfer member; and a cleaning mechanism for removing residual toner on the electrophotographic photoreceptor, wherein the image forming apparatus has a lubricant applying mechanism for applying a lubricant to a surface of the electrophotographic photoreceptor, and the electrophotographic photoreceptor is the electrophotographic photoreceptor.
In the image forming apparatus of the present invention, the charging mechanism is preferably a contact or non-contact roller charging type charging mechanism.
An image forming method according to the present invention includes: a charging step of charging the surface of the electrophotographic photoreceptor; an exposure step of forming an electrostatic latent image on the surface of the electrophotographic photoreceptor; a developing step of developing the electrostatic latent image with a developer containing a toner to form a toner image; a transfer step of transferring the toner image to a transfer material; a fixing step of fixing the toner image transferred to the transfer member; and a cleaning step of removing residual toner on the electrophotographic photoreceptor, wherein the developer contains a lubricant and the electrophotographic photoreceptor is used as the electrophotographic photoreceptor.
In the image forming method of the present invention, it is preferable that the charging step is performed by a contact or non-contact roller charging method.
The electrophotographic photoreceptor of the present invention is an electrophotographic photoreceptor having a photosensitive layer formed on a conductive support and a surface layer formed on the photosensitive layer, wherein the surface layer is formed by polymerizing a compound having two or more radical polymerizable functional groups, and contains inorganic fine particles at least a part of the surface of which is formed of a metal oxide and organic resin fine particles made of a resin containing a constituent unit derived from at least one of melamine and benzoguanamine, and the organic resin fine particles are organic resin fine particles subjected to a surface treatment with a coupling agent.
In the electrophotographic photoreceptor of the present invention, the organic resin fine particles preferably have a number average primary particle diameter of 100nm to 1500 nm.
In the electrophotographic photoreceptor of the present invention, the coupling agent is preferably a coupling agent containing at least fluorine element.
In the electrophotographic photoreceptor of the present invention, the inorganic fine particles preferably have a number average primary particle diameter of 10nm to 300 nm.
In the electrophotographic photoreceptor of the present invention, the inorganic fine particles are preferably composed of at least 1 of tin oxide and titanium oxide.
In the electrophotographic photoreceptor of the present invention, the inorganic fine particles are preferably composite fine particles in which a metal oxide is attached to the surface of a core material as a covering material.
In the composite fine particles, the core material is preferably composed of at least 1 of alumina, barium sulfate, and silica.
In the composite fine particles, the covering material is preferably composed of at least 1 of tin oxide and titanium oxide.
In the electrophotographic photoreceptor of the present invention, the radical polymerizable functional group is preferably an acryloyl group or a methacryloyl group.
The method for producing an electrophotographic photoreceptor is a method for producing an electrophotographic photoreceptor in which a photosensitive layer is formed on a conductive support and a surface layer is formed on the photosensitive layer, and the method for producing an electrophotographic photoreceptor is characterized by comprising a step of applying a surface layer forming coating liquid containing a compound having two or more radical polymerizable functional groups, inorganic fine particles at least a part of the surface of which is formed of a metal oxide, and organic resin fine particles surface-treated with a coupling agent and formed of a resin containing a constituent unit derived from at least one of melamine and benzoguanamine to the photosensitive layer to form a coating film and curing the coating film.
An image forming apparatus according to the present invention includes: an electrophotographic photoreceptor; a charging mechanism for charging the surface of the electrophotographic photoreceptor; an exposure mechanism for forming an electrostatic latent image on the surface of the electrophotographic photoreceptor; a developing mechanism for developing the electrostatic latent image with a developer containing a toner to form a toner image; a transfer mechanism for transferring the toner image to a transfer material; a fixing mechanism for fixing the toner image transferred to the transfer member; and a cleaning mechanism for removing residual toner on the electrophotographic photoreceptor, wherein the cleaning mechanism is composed of a blade, and the electrophotographic photoreceptor is the electrophotographic photoreceptor.
According to the electrophotographic photoreceptor of the present invention, the cured resin constituting the surface layer contains fine organic resin particles and fine metal oxide particles, the fine organic resin particles being composed of a resin containing a constituent unit derived from at least one of melamine and benzoguanamine, and the fine organic resin particles having a particle diameter in a predetermined range, whereby the electrophotographic photoreceptor has excellent cleanability and can suppress the occurrence of density unevenness of an image to be formed.
According to the image forming apparatus of the present invention, since the electrophotographic photoreceptor described above is provided, excellent cleaning performance is obtained, and thus it is possible to form a high-quality image for a long period of time, and even when the supply unevenness of the lubricant occurs, it is possible to suppress the occurrence of the image density unevenness associated therewith.
According to the image forming method of the present invention, since good cleanability is obtained by using the electrophotographic photoreceptor, it is possible to form a high-quality image for a long period of time, and also, when the supply unevenness of the lubricant occurs, the occurrence of the image density unevenness accompanying this is suppressed.
According to the electrophotographic photoreceptor of the present invention, the cured resin constituting the surface layer contains inorganic fine particles at least a part of the surface of which is formed of a metal oxide and organic resin fine particles made of a resin containing a constituent unit derived from at least one of melamine and benzoguanamine, and the organic resin fine particles are surface-treated with a coupling agent, and thus the electrophotographic photoreceptor can have good cleaning properties and high durability.
According to the method for producing an electrophotographic photoreceptor of the present invention, since aggregation of organic resin fine particles and inorganic fine particles is suppressed in the coating liquid for forming a surface layer, the photoreceptor can be reliably produced.
According to the image forming apparatus of the present invention, by having the electrophotographic photoreceptor, it is possible to form a high-quality image for a long period of time.
Drawings
Fig. 1 is a cross-sectional view for explaining an example of the layer structure in the photoreceptor of the present invention.
Fig. 2 is a cross-sectional view for explaining an example of the configuration of a circular slide hopper (slide hopper) coating apparatus used in the method for manufacturing a photoreceptor of the present invention.
Fig. 3 is a perspective cross-sectional view of the circular slide hopper coating apparatus shown in fig. 2.
Fig. 4 is a sectional view for explaining a configuration of an example of an image forming apparatus according to the present invention.
Fig. 5 is a cross-sectional view for explaining a configuration of an example of an image forming unit in the image forming apparatus according to the present invention.
Fig. 6 is a cross-sectional view for explaining a configuration of an example of a cleaning mechanism in the image forming apparatus according to the present invention.
Fig. 7A shows an evaluation image used for evaluation of the example.
Fig. 7B shows an evaluation image used in the evaluation of the example.
Fig. 8 is a schematic diagram for explaining the configuration of an apparatus for producing composite fine particles used in the examples.
Detailed Description
The present invention will be described in detail below.
[ electrophotographic photoreceptor ]
The photoreceptor of the present invention is not particularly limited as long as it is a photoreceptor in which a photosensitive layer and a surface layer are sequentially laminated on a conductive support, and specific examples thereof include the following layer configurations (1) and (2).
(1) The charge generating layer and the charge transporting layer are laminated in this order as an intermediate layer and a photosensitive layer on a conductive support.
(2) The layer structure is formed by sequentially laminating a single layer containing a charge generating substance and a charge transporting substance and a surface layer on a conductive support as an intermediate layer and a photosensitive layer.
Fig. 1 is a cross-sectional view for explaining an example of the layer structure in the photoreceptor of the present invention. Specifically, the layer structure of (1) above is shown. In this photoreceptor, a photosensitive layer 102 is laminated on a conductive support 101 via an intermediate layer 103, and a surface layer 106 is laminated on the photosensitive layer 102. The photosensitive layer 102 is composed of a charge generation layer 104 stacked on the intermediate layer 103, and a charge transport layer 105 stacked on the charge generation layer 104. The surface layer 106 contains organic resin fine particles 107a and metal oxide fine particles (or inorganic fine particles) 107 b.
The photoreceptor of the present invention is an organic photoreceptor, and the organic photoreceptor is an electrophotographic photoreceptor in which at least one of the charge generation function and the charge transport function, which are indispensable for the structure of the electrophotographic photoreceptor, is embodied by an organic compound, and includes a photoreceptor composed of a known organic charge generation substance or organic charge transport substance, a photoreceptor composed of a polymer complex for the charge generation function and the charge transport function, and the like.
The photoreceptor of the present invention is a negative charging type photoreceptor. When the surface of the negatively charged photoreceptor is charged to a negative level and then exposed to light, charges are generated in the charge generation layer (photosensitive layer in the case of a single layer), in which negative charges (electrons) move to the conductive support via the intermediate layer, while holes (holes) move to the surface of the organic photoreceptor via the charge transport layer (photosensitive layer), and the negative charges on the surface are cancelled out to form an electrostatic latent image.
[ surface layer ]
The first surface layer constituting the photoreceptor of the present invention is a surface layer comprising a cured resin obtained by polymerizing a compound having two or more radical polymerizable functional groups, organic resin fine particles and metal oxide fine particles, the organic resin fine particles being composed of a resin containing a constituent unit derived from at least one of melamine and benzoguanamine and having a number average primary particle diameter of 0.01 to 3.00. mu.m.
The second surface layer constituting the photoreceptor of the present invention is a surface layer comprising inorganic fine particles at least a part of the surface of which is formed of a metal oxide and organic resin fine particles made of a resin containing a constituent unit derived from at least one of melamine and benzoguanamine, the cured resin obtained by polymerizing a compound having two or more radical polymerizable functional groups, and the organic resin fine particles are surface-treated with a coupling agent.
At least a part of the surface of the inorganic fine particles is formed of a metal oxide, and may be formed of a single material or a plurality of materials.
In the photoreceptor of the present invention, since the surface layer is made of a cured resin, basically, a high film strength can be obtained, and further, a high film strength can be obtained by containing inorganic fine particles in the cured resin. Therefore, high durability can be obtained. Further, the organic resin fine particles are subjected to surface treatment with a coupling agent, whereby aggregation of the organic resin fine particles and the inorganic fine particles can be suppressed in the coating liquid for forming the surface layer prepared in the production process of the photoreceptor. In addition, on the surface layer formed by applying the coating liquid for forming the surface layer on the photosensitive layer and carrying out curing treatment, the aggregate of the organic resin fine particles and the inorganic fine particles can be reduced. Therefore, the characteristics of the organic resin fine particles can be effectively expressed. As described above, according to the photoreceptor of the present invention, good cleaning property can be obtained while obtaining high durability.
Here, it is considered that the aggregation of the organic resin fine particles and the inorganic fine particles can be suppressed by surface-treating the inorganic fine particles with the coupling agent, but if the inorganic fine particles are surface-treated inorganic fine particles, the electrical characteristics of the photoreceptor may be degraded. Therefore, by surface-treating the organic resin fine particles with the coupling agent as in the present invention, aggregates in the surface layer can be reduced and the function as a photoreceptor can be ensured.
(curing resin)
The cured resin is a main component constituting the surface layer. The cured resin is obtained by polymerizing a compound having two or more radically polymerizable functional groups (hereinafter, also referred to as "polyfunctional radically polymerizable compound"). Specifically, the cured resin is formed by polymerizing and curing a polyfunctional radical polymerizable compound by irradiation with actinic rays such as ultraviolet rays and electron beams.
As the monomer for forming the cured resin, a polyfunctional radical polymerizable compound is used, but a compound having one radical polymerizable functional group (hereinafter, also referred to as "monofunctional radical polymerizable compound") may be used together. When a monofunctional radical polymerizable compound is used, the proportion thereof is preferably 0 to 30% by mass relative to the total amount of monomers for forming the cured resin.
Examples of the radical polymerizable functional group include a vinyl group, an acryloyl group, and a methacryloyl group.
The polyfunctional radical polymerizable compound is preferably a compound having two or more acryloyl groups (CH) as the radical polymerizable functional group, because it can be cured in a short time and with a small amount of light2CHCO-) or methacryloyl (CH)2＝CCH3CO-) or oligomers thereof. Therefore, as the curing resin, an acrylic resin formed of an acrylic monomer or an oligomer thereof is preferable.
In the present invention, the polyfunctional radical polymerizable compound may be used alone or in combination. These polyfunctional radical polymerizable compounds may be used in the form of monomers or oligomers.
Specific examples of the polyfunctional radical polymerizable compound are shown below.
[ chemical formula 1 ]
[ chemical formula 2 ]
Wherein, in the above chemical formulae representing the exemplary compounds (M1) to (M14), R represents an acryloyl group (CH)2-CHCO-), R' represents methacryloyl (CH)2＝CCH3CO－)。
(organic resin Fine particles)
The organic resin fine particles are composed of a resin containing a constituent unit derived from at least one of melamine and benzoguanamine (hereinafter, also referred to as "untreated organic resin fine particles"). Specific examples of such resins include melamine resins such as polycondensates of melamine and formaldehyde, and copolycondensates of melamine, benzoguanamine, and formaldehyde; and a benzoguanamine resin such as a polycondensate of benzoguanamine and formaldehyde.
The organic resin fine particles are preferably a condensation product of melamine and formaldehyde from the viewpoints of toner cleanability and suppression of image density unevenness.
By containing the organic resin fine particles in the surface layer, the surface of the photoreceptor can be appropriately roughened, and good cleanability can be ensured. Further, since the organic resin fine particles are fine particles having a small van der waals force, the adhesion force with the toner can be reduced, and the cleanability can be improved.
The organic resin fine particles have a number average primary particle diameter of 0.01 to 3.00. mu.m, preferably 0.1 to 1.5 μm. More preferably 0.2 to 1.0 μm.
When the number-average secondary particle diameter of the organic resin fine particles is within the above range, the surface of the photoreceptor can be appropriately roughened, and good cleanability can be ensured.
In the present invention, the number-average primary particle diameter of the organic resin fine particles is measured as follows.
First, as a measurement sample, a photosensitive layer including a surface layer is cut out from the surface of a photoreceptor with a knife or the like, and is stuck to an arbitrary holder with the cut surface facing upward.
Then, the calculation is performed based on a photographic image obtained by observing and capturing a measurement sample with a scanning electron microscope. The photograph was taken with the microscope set at a magnification of 3 ten thousand, and 100 microparticles were randomly extracted from the photograph image and calculated. Specifically, a photograph image was binarized by an automatic image processing analyzer "LUZEX AP" (manufactured by nile corporation), and the horizontal ferlet diameter of 100 fine particles was measured to calculate an average value, which was set as a number-uniform secondary particle diameter.
In the present invention, by containing the organic resin fine particles in the surface layer, appropriate surface roughness can be imparted to the surface of the photoreceptor, and good cleanability can be ensured. Further, the melamine resin and the benzoguanamine resin are positively chargeable resins, and the charging sequence of the resin, the negatively chargeable toner, and the lubricant is "negatively chargeable toner" "lubricant (e.g., zinc stearate)" "melamine resin and benzoguanamine resin", so even if the supply unevenness of the lubricant occurs, the contact charging of the surface of the photoreceptor containing the organic resin fine particles and the negatively chargeable toner is more advantageous than the contact charging of the negatively chargeable toner and the lubricant, and the occurrence of potential unevenness due to the contact charging of the toner and the lubricant can be prevented, and the occurrence of density unevenness in the formed image can be suppressed.
The organic resin fine particles are preferably contained in a proportion of 5 to 50 parts by mass, more preferably 5 to 40 parts by mass, and particularly preferably 10 to 30 parts by mass, relative to 100 parts by mass of the cured resin.
When the content ratio of the organic resin fine particles is within the above range, the organic resin fine particles are exposed on the surface of the photoreceptor in relation to the number-average primary particle diameter, and even when the supply unevenness of the lubricant occurs, the contact electrification between the surface of the photoreceptor including the organic resin fine particles and the negatively chargeable toner is dominant, and the occurrence of the density unevenness of the image due to the supply unevenness of the lubricant can be reliably suppressed.
If the content ratio of the organic resin fine particles is too large, the desired latent image may not be formed due to the decrease in light transmittance. On the other hand, when the content ratio of the organic resin fine particles is too small, the cleaning property is deteriorated due to the reduction of the surface roughness, and when the lubricant adhesion unevenness is generated on the surface of the photoreceptor, the image density unevenness may be caused.
As the organic resin fine particles, products sold by melamine resin (a condensation product of melamine and formaldehyde) "EPOSTAR S", "EPOSTAR S6", benzoguanamine resin (a condensation product of benzoguanamine and formaldehyde) "EPOSTAR" (manufactured by japan catalyst corporation, mentioned above), and the like can be used.
The organic resin fine particles may be those obtained by surface-treating the surfaces of fine particles of a resin containing a constituent unit derived from at least one of melamine and benzoguanamine (the above-mentioned untreated organic resin fine particles) with a coupling agent.
The organic resin fine particles are surface-treated with a coupling agent, so that the surfaces of the organic resin fine particles are reformed, and aggregation of the organic resin fine particles and the inorganic fine particles can be suppressed in a coating liquid for surface layer formation, which is prepared in a process for producing a photoreceptor described later.
Examples of the coupling agent include a silane coupling agent.
The silane coupling agent is a coupling agent having two or more methoxy groups or ethoxy groups, and has a molecular weight of 100 to 1500, preferably 200 to 1000.
The coupling agent is preferably a coupling agent containing fluorine. Specifically, the preferred coupling agent has 1 to 10 CF2More preferably 2 to 8.
The coupling agent containing fluorine can further reduce the adhesion of the organic resin fine particles to the toner. The reason for this is considered to be that the coupling agent containing a fluorine element has a function of neutralizing the positive charge of the organic resin fine particles.
Specific examples of the coupling agent are shown below.
C－1：CF3CF2CF2CF2CF2CF2CF2CF2CH2CH2Si(OCH2CH3)3
C－2：CF3CF2CF2CF2CF2CF2CF2CF2CH2CH2Si(OCH3)3
C－3：CF3CF2CF2CF2CF2CF2CH2CH2Si(OCH2CH3)3
C－4：CF3CF2CF2CF2CF2CF2CH2CH2Si(OCH3)3
C－5：CF3CF2CF2CF2CF2CH2CH2Si(OCH2CH3)3
C－6：CF3CF2CF2CF2CH2CH2Si(OCH3)3
C－7：CF3CH2CH2Si(OCH3)3
C－8：CH2＝C(CH3)COO(CH2)3Si(OCH3)3
[ chemical formula 3 ]
The coupling agent may be used alone in 1 kind or in a mixture of 2 or more kinds.
The amount of the coupling agent to be treated is preferably 5 to 90% by mass, more preferably 10 to 70% by mass, based on the untreated organic resin fine particles.
The surface treatment method of the coupling agent is not particularly limited, and wet treatment may be employed. As a surface treatment method by wet treatment, specifically, a method of mixing and stirring a solution in which untreated organic resin fine particles and a coupling agent are dispersed in a solvent at a predetermined temperature, removing the solvent, and powdering the mixture is mentioned. The treatment temperature is, for example, 20 to 60 ℃ and the mixing time is, for example, 30 to 60 minutes. In this case, an acid such as hydrochloric acid or sulfuric acid may be added as a catalyst. The obtained powder may be dried at 80 to 150 ℃ for 30 to 90 minutes.
In the present invention, the coupling agent applied to the surface of the organic resin fine particles can be detected by functional evaluation based on infrared absorption analysis (IR) and weight loss based on thermogravimetric analysis (TG).
(Metal oxide Fine particles)
The metal oxide fine particles are not particularly limited, and for example, silica (silicon oxide), magnesia, zinc oxide, lead oxide, alumina (aluminum oxide), zirconia, tin oxide, titania (titanium oxide), niobium oxide, molybdenum oxide, vanadium oxide, or the like can be used, and among them, tin oxide is preferable from the viewpoint of hardness, electrical conductivity, and light transmittance.
The number average primary particle diameter of the metal oxide fine particles is preferably 1 to 300nm, more preferably 3 to 100nm, and still more preferably 5 to 40 nm.
In the present invention, the number-average primary particle diameter of the metal oxide fine particles is measured as follows.
First, as a measurement sample, a photosensitive layer including a surface layer is cut out from the surface of a photoreceptor with a knife or the like, and is attached to an arbitrary holder so that the cut surface faces upward. Then, the measurement sample was photographed at 10000 times magnification by a scanning electron microscope (manufactured by japan electronics). The number average primary particle size was calculated using an automatic image processing analyzer "LUZEX AP (software version ver.1.32)" (manufactured by nile corporation) on photographic images (excluding agglutinated particles) of 300 particles randomly acquired by a scanner.
Preferably, the metal oxide fine particles are surface-treated with a surface treatment agent comprising a compound having a radical polymerizable functional group.
Specifically, it is preferable that the metal oxide fine particles are surface-treated with a surface treatment agent comprising a compound having a radical polymerizable functional group to introduce the radical polymerizable functional group to the surface of the metal oxide fine particles.
Since the metal oxide fine particles are surface-treated with the surface treatment agent comprising the compound having a radical polymerizable functional group, they can react with the radical polymerizable compound to form a crosslinked structure in the step of forming the surface layer in the process of producing the photoreceptor, which will be described later, and a sufficient film strength of the surface layer can be obtained. In addition, the metal oxide fine particles in the cured resin attain high dispersibility.
Examples of the radical polymerizable functional group in the surface treatment agent include a vinyl group, an acryloyl group, and a methacryloyl group. Such a radical polymerizable functional group can react with a radical polymerizable compound forming a cured resin to form a surface layer having a high film strength. The surface treatment agent having a radical polymerizable functional group is preferably a silane coupling agent having a polymerizable functional group such as a vinyl group, an acryloyl group, or a methacryloyl group.
Specific examples of the surface treatment agent composed of a compound having a radical polymerizable functional group are shown below.
S－1：CH2＝CHSi(CH3)(OCH3)2
S－2：CH2＝CHSi(OCH3)3
S－3：CH2＝CHSiCl3
S－4：CH2＝CHCOO(CH2)2Si(CH3)(OCH3)2
S－5：CH2＝CHCOO(CH2)2Si(OCH3)3
S－6：CH2＝CHCOO(CH2)2Si(OC2H5)(OCH3)2
S－7：CH2＝CHCOO(CH2)3Si(OCH3)3
S－8：CH2＝CHCOO(CH2)2Si(CH3)Cl2
S－9：CH2＝CHCOO(CH2)2SiCl3
S－10：CH2＝CHCOO(CH2)3Si(CH3)Cl2
S－11：CH2＝CHCOO(CH2)3SiCl3
S－12：CH2＝C(CH3)COO(CH2)2Si(CH3)(OCH3)2
S－13：CH2＝C(CH3)COO(CH2)2Si(OCH3)3
S－14：CH2＝C(CH3)COO(CH2)3Si(CH3)(OCH3)2
S－15：CH2＝C(CH3)COO(CH2)3Si(OCH3)3
S－16：CH2＝C(CH3)COO(CH2)2Si(CH3)Cl2
S－17：CH2＝C(CH3)COO(CH2)2SiCl3
S－18：CH2＝C(CH3)COO(CH2)3Si(CH3)Cl2
S－19：CH2＝C(CH3)COO(CH2)3SiCl3
S－20：CH2＝CHSi(C2H5)(OCH3)2
S－21：CH2＝C(CH3)Si(OCH3)3
S－22：CH2＝C(CH3)Si(OC2H5)3
S－23：CH2＝CHSi(OCH3)3
S－24：CH2＝C(CH3)Si(CH3)(OCH3)2
S－25：CH2＝CHSi(CH3)Cl2
S－26：CH2＝CHCOOSi(OCH3)3
S－27：CH2＝CHCOOSi(OC2H5)3
S－28：CH2＝C(CH3)COOSi(OCH3)3
S－29：CH2＝C(CH3)COOSi(OC2H5)3
S－30：CH2＝C(CH3)COO(CH2)3Si(OC2H5)3
S－31：CH2＝CHCOO(CH2)2Si(CH3)2(OCH3)
S－32：CH2＝CHCOO(CH2)2Si(CH3)(OCOCH3)2
S－33：CH2＝CHCOO(CH2)2Si(CH3)(ONHCH3)2
S－34：CH2＝CHCOO(CH2)2Si(CH3)(OC6H5)2
S－35：CH2＝CHCOO(CH2)2Si(C10H21)(OCH3)2
S－36：CH2＝CHCOO(CH2)2Si(CH2C6H5)(OCH3)2
Further, as the surface-treating agent, a silane compound having a reactive organic group capable of radical polymerization may be used in addition to the surface-treating agents shown in the above exemplified compounds (S-1) to (S-36).
The surface treatment agent can be used in 1 kind alone or in a mixture of 2 or more kinds.
The amount of the surface treatment agent to be treated is preferably 0.1 to 200 parts by mass, more preferably 7 to 70 parts by mass, per 100 parts by mass of the untreated metal oxide fine particles.
As a method for treating the surface treatment agent with respect to the untreated metal oxide fine particles, for example, a method of wet-pulverizing a slurry (suspension of solid particles) containing the untreated metal oxide fine particles and the surface treatment agent may be mentioned. By this method, the surface treatment of the metal oxide fine particles can be performed while preventing the metal oxide fine particles from reagglomerating. Then, the solvent was removed to obtain powder.
Examples of the surface treatment device include a wet medium dispersion type device. The wet medium dispersion type apparatus has a step of filling beads (beads) as a medium into a container and crushing and dispersing aggregated particles of metal oxide fine particles by rotating a stirring plate attached perpendicularly to a rotating shaft at a high speed, and is not limited as long as the metal oxide fine particles are sufficiently dispersed and surface-treated when the metal oxide fine particles are surface-treated, and various types such as a vertical type, a horizontal type, a continuous type, and a batch type can be used. Specifically, a sand mill, a glass bead mill, a pearl mill, a grain mill, a dinoteur mill, a stirring mill, a dynamic mill, or the like can be used. These dispersion-type apparatuses finely pulverize and disperse by impact crushing, friction, shearing, shear stress, and the like using a pulverizing medium (medium) such as balls or beads.
As the beads used in the wet medium dispersion type device, spheres made of glass, alumina, zircon, zirconia, steel, flint, or the like can be used, and spheres made of zirconia or zircon are particularly preferable. The beads are generally about 1 to 2mm in diameter, but about 0.1 to 1.0mm is preferably used in the present invention.
Various materials such as stainless steel, nylon, and ceramics can be used for the disk (disk) and the inner wall of the container used in the wet medium dispersion type apparatus, and a disk and an inner wall of the container made of ceramics such as zirconia and silicon carbide are particularly preferable in the present invention.
The metal oxide fine particles are preferably contained in an amount of 60 to 100 parts by mass, more preferably 70 to 90 parts by mass, based on 100 parts by mass of the cured resin.
When the content ratio of the metal oxide fine particles is within the above range, hardness, conductivity, and light transmittance can be sufficiently satisfied.
When the content ratio of the metal oxide fine particles is too large, the reduction in light transmittance affects the formation of a latent image, and there is a problem of image defects and the like due to aggregation. On the other hand, when the content ratio of the metal oxide fine particles is too small, there is a possibility that deterioration in abrasion resistance due to reduction in hardness and density unevenness at the time of high-speed printing due to reduction in sensitivity may occur.
The metal oxide fine particles are composed of a single material as described above, but may be composed of a single material or a plurality of materials as long as they are inorganic fine particles each having at least a part of the surface thereof composed of a metal oxide.
(inorganic Fine particles)
The inorganic fine particles are inorganic fine particles at least a part of the surface of which is formed of a metal oxide, and may be formed of a single material or a plurality of materials. As the inorganic fine particles composed of a plurality of materials, specifically, composite fine particles having a core-shell structure in which a metal oxide is attached as a covering material to the surface of a core material can be exemplified. The core-shell structured composite fine particles may be exposed to a part of the surface of the core material, or the surface of the core material may be completely covered with a covering material.
Examples of the inorganic fine particles made of a single material include fine particles of silicon oxide (silica), magnesium oxide, zinc oxide, lead oxide, aluminum oxide (alumina dioxide), zirconium oxide, tin oxide, titanium oxide (titania), niobium oxide, molybdenum oxide, vanadium oxide, and the like. Among them, titanium oxide and tin oxide are preferable from the viewpoint of hardness, conductivity, and light transmittance.
In the case where the inorganic fine particles are composite fine particles having a core-shell structure, an insulating material may be used as the core material, and specific examples thereof include barium sulfate, silica, and alumina. Barium sulfate is particularly preferable as the core material from the viewpoint of light transmittance. Examples of the metal oxide as the covering material include tin oxide, titanium oxide, zinc oxide, zirconium oxide, and indium tin oxide.
The amount of the metal oxide adhering to the core material is preferably 30 to 80 mass%, more preferably 40 to 70 mass%, based on the core material.
As a method for attaching the metal oxide as the covering material to the core material, for example, a method disclosed in japanese patent application laid-open No. 2009-255042 and the like can be used.
As described above, the composite fine particles having a core-shell structure of inorganic fine particles can increase the particle diameter while securing electrical conductivity and light transmittance, and thus can improve the stability of electrical characteristics and the film strength.
The volume resistivity of the inorganic fine particles is preferably 10-3～107[ omega cm ], more preferably 10-1～105〔Ωcm〕。
The volume resistivity is a value measured by a TR8611A digital super insulation resistance/microammeter manufactured by Wutian institute of technology, Inc. under an environment of 23 ℃ and 50% humidity.
The number average primary particle diameter of the inorganic fine particles is preferably 10 to 300nm, more preferably 20 to 250 nm.
When the particle diameter of the inorganic fine particles is within the above range, a sufficiently high film strength can be ensured.
In the present invention, the number-average primary particle diameter of the inorganic fine particles is measured as follows.
First, a measurement sample is prepared by cutting out the photosensitive layer including the surface layer from the surface of the photoreceptor with a knife or the like, and attaching the cut surface to an arbitrary holder so as to face upward. Then, the measurement sample was photographed at 10000 times magnification by a scanning electron microscope (manufactured by japan electronics). The number average primary particle size was calculated using an automatic image processing analyzer "LUZEX AP (software version ver.1.32)" (manufactured by nile corporation) on photographic images (excluding agglutinated particles) of 300 particles randomly acquired by a scanner.
The inorganic fine particles are preferably contained in a proportion of 50 to 200 parts by mass, more preferably 70 to 150 parts by mass, relative to 100 parts by mass of the cured resin.
When the content ratio of the inorganic fine particles is within the above range, hardness, conductivity, and light transmittance can be sufficiently satisfied.
(Charge-transporting Compound)
The surface layer preferably contains a charge transporting compound.
The charge transporting compound is not particularly limited as long as it has charge transporting performance for transporting charge carriers in the surface layer, and is particularly preferably a compound represented by the following general formula (1).
In the photoreceptor of the present invention, a sufficient response can be ensured even at the time of high-speed printing by containing a charge transporting compound in the surface layer.
The charge transporting compound used in the present invention is a compound which is unreactive with a surface treatment agent comprising a polyfunctional radical polymerizable compound or a compound having a radical polymerizable functional group.
[ chemical formula 4 ]
In the general formula (1), R1And R2Each independently a hydrogen atom or a methyl group. In addition, R3The alkyl group is a linear or branched alkyl group having 1 to 5 carbon atoms, and preferably a propyl group, a pentyl group, or a butyl group.
Specific examples of the compounds represented by the above general formula (1) are shown below.
[ chemical formula 5 ]
[ chemical formula 6 ]
[ chemical formula 7 ]
The compound represented by the general formula (1) can be synthesized by a known synthesis method, for example, a method disclosed in Japanese patent laid-open No. 2006-143720 and the like.
The charge transporting compound is preferably contained in an amount of 10 to 30 parts by mass, more preferably 15 to 25 parts by mass, based on 100 parts by mass of the cured resin.
When the content ratio of the charge transporting compound is within the above range, sufficient responsiveness can be secured even in high-speed printing.
If the content ratio of the charge transporting compound is too large, the film strength of the surface layer may be reduced, and the photoreceptor life may be shortened. On the other hand, when the content ratio of the charge transporting compound is too small, the amount of hole traps generated in the surface layer increases, and electrostatic image density unevenness is likely to occur.
The surface layer according to the present invention may contain other components in addition to the cured resin, the organic resin fine particles, the metal oxide fine particles (or the inorganic fine particles), and the charge transporting compound, and may contain, for example, various antioxidants, and various lubricant particles such as fluorine atom-containing resin particles. The fluorine atom-containing resin particles are preferably 1 or 2 or more selected from tetrafluoroethylene resin, chlorotrifluoroethylene resin, hexafluorovinylchloroethylene propylene resin, vinyl fluoride resin, vinylidene fluoride resin, difluorodichloroethylene resin, and copolymers thereof, and particularly preferably tetrafluoroethylene resin and vinylidene fluoride resin.
The thickness of the surface layer is preferably 0.2 to 10 μm, more preferably 0.5 to 6 μm.
Hereinafter, the structure of the photoreceptor other than the surface layer will be described as the layer structure of the above (1).
[ conductive support ]
The conductive support constituting the photoreceptor of the present invention may have conductivity, and examples thereof include a support formed by laminating a metal such as aluminum, copper, chromium, nickel, zinc, or stainless steel in a drum or sheet form, a support formed by laminating a metal foil such as aluminum or copper on a plastic film, a support formed by vapor-depositing aluminum, indium oxide, tin oxide, or the like on a plastic film, and a metal, plastic film, paper, or the like, in which a conductive layer is provided by coating a conductive material alone or together with a binder resin.
[ intermediate layer ]
In the photoreceptor of the present invention, an intermediate layer having a barrier function and an adhesive function may be provided between the conductive support and the photosensitive layer. In view of preventing various failures, it is preferable to provide an intermediate layer.
Such an intermediate layer contains, for example, a binder resin (hereinafter also referred to as "intermediate layer binder resin") and, if necessary, conductive particles and metal oxide particles.
Examples of the binder resin for the intermediate layer include casein, polyvinyl alcohol, nitrocellulose, an ethylene-acrylic acid copolymer, a polyamide resin, a polyurethane resin, and gelatin. Among these, alcohol-soluble polyamide resins are preferred.
For the purpose of resistance adjustment, various conductive particles and metal oxide particles may be contained in the intermediate layer. For example, various metal oxide particles such as aluminum oxide, zinc oxide, titanium oxide, tin oxide, antimony oxide, indium oxide, and bismuth oxide can be used. Tin-doped indium oxide, antimony-doped tin oxide, zirconium oxide, and other ultrafine particles can be used.
The number-average primary particle diameter of the metal oxide particles is preferably 0.3 μm or less, more preferably 0.1 μm or less.
These metal oxide particles may be used alone in 1 kind or in a mixture of 2 or more kinds. When 2 or more kinds are mixed, the mixture may be in the form of a solid solution or a melt.
The content of the conductive particles or the metal oxide particles is preferably 20 to 400 parts by mass, more preferably 50 to 350 parts by mass, per 100 parts by mass of the binder resin.
The thickness of the intermediate layer is preferably 0.1 to 15 μm, more preferably 0.3 to 10 μm.
[ Charge generation layer ]
The charge generation layer in the photosensitive layer constituting the photoreceptor of the present invention contains a charge generation substance and a binder resin (hereinafter, also referred to as "binder resin for charge generation layer").
Examples of the charge generating substance include azo raw materials such as sudan red and daidzein (Diane Blue), quinone pigments such as pyrene and anthanthrone, quinoline cyanine pigments, perylene pigments, indigo pigments such as indigo and thioindigo, polycyclic quinone pigments such as pyranthrone and diphosphhthalpyrene, and phthalocyanine pigments, but are not limited thereto. Among these, polycyclic quinone pigments, TITANYL PHTHALOCYANINE (TITANYL PHTHALOCYANINE) pigments are preferable.
These charge generating substances may be used alone in 1 kind or in combination of 2 or more kinds.
As the binder resin for the charge generating layer, known resins can be used, and examples thereof include, but are not limited to, polystyrene resins, polyethylene resins, polypropylene resins, acrylic resins, methacrylic resins, vinyl chloride resins, vinyl acetate resins, polyvinyl butyral resins, epoxy resins, polyurethane resins, phenol resins, polyester resins, alkyd resins, polycarbonate resins, silicone resins, melamine resins, and copolymer resins containing two or more of these resins (for example, vinyl chloride-vinyl acetate copolymer resins, vinyl chloride-vinyl acetate-maleic anhydride copolymer resins), polyvinyl carbazole resins, and the like. Among these, a polyvinyl butyral resin is preferred.
The content of the charge generating substance in the charge generating layer is preferably 1 to 600 parts by mass, more preferably 50 to 500 parts by mass, per 100 parts by mass of the binder resin for the charge generating layer.
The thickness of the charge generation layer varies depending on the properties of the charge generation substance, the properties of the binder resin for the charge generation layer, the content ratio, and the like, and is preferably 0.01 to 5 μm, and more preferably 0.05 to 3 μm.
[ Charge transport layer ]
The charge transport layer in the photosensitive layer constituting the photoreceptor of the present invention is a layer containing a charge transport material and a binder resin (hereinafter, also referred to as "binder resin for charge transport layer").
Examples of the charge transport substance of the charge transport layer include substances that transport charges, such as triphenylamine derivatives, hydrazone compounds, styrene compounds, benzidine compounds, and butadiene compounds.
As the binder resin for the charge transport layer, known resins can be used, and examples thereof include polycarbonate resins, polyacrylic resins, polyester resins, polystyrene resins, styrene-acrylonitrile copolymer resins, polymethacrylate resins, styrene-methacrylate copolymer resins, and the like, but polycarbonate resins are preferred. In addition, in the cracking resistance, abrasion resistance, charged characteristics, preferably BPA (bisphenol A) type, BPZ (bisphenol Z) type, two methyl BPA type, BPA-two methyl BPA copolymer type polycarbonate resin.
The content of the charge transport material in the charge transport layer is preferably 10 to 500 parts by mass, more preferably 20 to 250 parts by mass, per 100 parts by mass of the binder resin for charge transport layer.
The thickness of the charge transport layer varies depending on the properties of the charge transport material, the properties and the content of the binder resin for the charge transport layer, and the like, and is preferably 5 to 40 μm, more preferably 10 to 30 μm.
An antioxidant, an electron conductive agent, a stabilizer, silicon oil, or the like may be added to the charge transport layer. The antioxidant is preferably an antioxidant disclosed in Japanese patent application laid-open No. 2000-305291, and the electron conductive agent is preferably an electron conductive agent disclosed in Japanese patent application laid-open Nos. 50-137543 and 58-76483.
According to the photoreceptor as described above, the cured resin constituting the surface layer contains the fine organic resin particles and the fine metal oxide particles, each of which is composed of at least one of melamine resin and benzoguanamine resin, and the fine organic resin particles have a particle diameter within a specific range, and thus the photoreceptor has good cleaning properties and can suppress the occurrence of density unevenness in an image formed.
[ method for producing photoreceptor ]
The photoreceptor of the present invention can be produced, for example, through the following steps.
Step (1): and a step of forming an intermediate layer by applying a coating liquid for forming the intermediate layer to the outer peripheral surface of the conductive support and drying the coating liquid.
Step (2): and a step of forming a charge generation layer by applying a coating liquid for forming a charge generation layer to the outer peripheral surface of the intermediate layer formed on the conductive support and drying the coating liquid.
Step (3): and a step of applying a coating liquid for forming a charge transport layer to the outer peripheral surface of the charge generation layer formed on the intermediate layer, and drying the coating liquid to form the charge transport layer.
Step (4): and a step of applying a coating liquid for forming a surface layer to the outer peripheral surface of the charge transport layer formed on the charge generation layer to form a coating film, and curing the coating film to form a surface layer.
[ step (1): formation of intermediate layer ]
The intermediate layer can be formed by dissolving a binder resin for the intermediate layer in a solvent to prepare a coating liquid (hereinafter also referred to as "coating liquid for forming an intermediate layer"), dispersing conductive particles and metal oxide particles as necessary, applying the coating liquid to a conductive support to form a coating film with a constant film thickness, and drying the coating film.
As a mechanism for dispersing the conductive particles and the metal oxide particles in the coating liquid for forming the intermediate layer, an ultrasonic disperser, a ball mill, a sand mill, a homomixer, or the like can be used, but the mechanism is not limited to these.
Examples of the coating method of the coating liquid for forming the intermediate layer include known methods such as a dip coating method, a spray coating method, a spin coating method, a bead coating method, a doctor blade coating method, an electron beam coating method, a slide hopper method, and a circular slide hopper method.
The method of drying the coating film may be appropriately selected depending on the type of solvent and the film thickness, but thermal drying is preferred.
The solvent used in the step of forming the intermediate layer may be any solvent that can disperse the conductive particles and the metal oxide particles well and dissolve the binder resin for the intermediate layer. Specifically, alcohols having 1 to 4 carbon atoms such as methanol, ethanol, n-propanol, isopropanol, n-butanol, t-butanol, and sec-butanol are preferable because they are excellent in solubility and coating properties of the binder resin. In addition, in order to improve storage stability and particle dispersibility, examples of a cosolvent that can be used together with the above solvent to obtain a preferable effect include benzyl alcohol, toluene, dichloromethane, cyclohexanone, tetrahydrofuran, and the like.
The concentration of the binder resin for the intermediate layer in the coating liquid for forming the intermediate layer can be appropriately selected in accordance with the layer thickness of the intermediate layer and the production speed.
[ step (2): formation of Charge Generation layer
The charge generating layer can be formed by preparing a coating liquid (hereinafter, also referred to as "charge generating layer forming coating liquid") by dispersing a charge generating substance in a solution in which a binder resin for the charge generating layer is dissolved in a solvent, applying the coating liquid to the intermediate layer at a constant film thickness to form a coating film, and drying the coating film.
As a mechanism for dispersing the charge generating substance in the charge generating layer forming coating liquid, for example, an ultrasonic dispersing machine, a ball mill, a sand mill, a homomixer, or the like can be used, but the mechanism is not limited to these.
Examples of the coating method of the coating liquid for forming the charge generation layer include known methods such as a dip coating method, a spray coating method, a spin coating method, a bead coating method, a doctor blade coating method, an electron beam coating method, a slide hopper method, and a circular slide hopper method.
The method of drying the coating film can be appropriately selected depending on the type of solvent and the film thickness, but thermal drying is preferred.
Examples of the solvent used for forming the charge generating layer include toluene, xylene, dichloromethane, 1, 2-dichloroethane, methyl ethyl ketone, cyclohexane, ethyl acetate, tert-butyl acetate, methanol, ethanol, propanol, butanol, methyl cellosolve, 4-methoxy-4-methyl-2-pentanone, ethyl cellosolve, tetrahydrofuran, and 1-bis (methylene chloride)Alkane, 1, 3-dioxolane, pyridine, diethylamine, etc., but are not limited thereto.
[ step (3): formation of Charge transport layer
The charge transport layer can be formed by preparing a coating liquid in which a binder resin for the charge transport layer and a charge transport substance are dissolved in a solvent (hereinafter, also referred to as "coating liquid for forming a charge transport layer"), coating the coating liquid on the charge generation layer to a constant film thickness to form a coating film, and drying the coating film.
Examples of the coating method of the coating liquid for forming the charge transport layer include known methods such as a dip coating method, a spray coating method, a spin coating method, a bead coating method, a doctor blade coating method, an electron beam coating method, a slide hopper method, and a circular slide hopper method.
The method of drying the coating film can be appropriately selected depending on the type of solvent and the film thickness, but thermal drying is preferred.
Examples of the solvent used for forming the charge transport layer include toluene, xylene, methylene chloride, 1, 2-dichloroethane, methyl ethyl ketone, cyclohexanone, ethyl acetate, butyl acetate, methanol, ethanol, propanol, butanol, tetrahydrofuran, and 1, 4-bis (ethylene glycol)Alkane, 1, 3-dioxolane, pyridine, diethylamine, etc., but are not limited theretoThese are described.
[ step (4): formation of surface layer ]
The surface layer can be formed by preparing a coating liquid (hereinafter, also referred to as "surface layer forming coating liquid") by adding a polyfunctional radical polymerizable compound, organic resin fine particles, metal oxide fine particles (or inorganic fine particles), a polymerization initiator, and other components as needed to a known solvent, applying the surface layer forming coating liquid to the outer peripheral surface of the charge transport layer formed in step (3) to form a coating film, drying the coating film, and irradiating actinic rays such as ultraviolet rays and electron beams to polymerize the radical polymerizable compound component in the coating film.
The surface layer is formed into a crosslinking-type cured resin by, for example, a reaction between the polyfunctional radical polymerizable compounds during the coating, drying, and curing, or a reaction between the radical polymerizable functional group of the surface treatment agent and the radical polymerizable functional group of the polyfunctional radical polymerizable compound when the metal oxide fine particles are surface-treated with the surface treatment agent composed of a compound having a radical polymerizable functional group.
In the coating liquid for forming the surface layer, the organic resin fine particles are preferably contained in a proportion of 5 to 50 parts by mass, more preferably 5 to 40 parts by mass, and particularly preferably 10 to 30 parts by mass, relative to 100 parts by mass of all monomers (polyfunctional radical polymerizable compound, monofunctional radical polymerizable compound) for forming the cured resin.
The metal oxide fine particles are preferably contained in an amount of 60 to 100 parts by mass, more preferably 70 to 90 parts by mass, based on 100 parts by mass of all the monomers (polyfunctional radical polymerizable compound, monofunctional radical polymerizable compound) for forming the cured resin.
The inorganic fine particles are preferably contained in a proportion of 50 to 200 parts by mass, more preferably 70 to 180 parts by mass, based on 100 parts by mass of all the monomers (polyfunctional radical polymerizable compound, monofunctional radical polymerizable compound) for forming the cured resin.
As a mechanism for dispersing the organic resin fine particles and the metal oxide fine particles (or the inorganic fine particles) in the coating liquid for forming the surface layer, an ultrasonic dispersing machine, a ball mill, a sand mill, a homomixer, or the like can be used, but the mechanism is not limited to these.
The solvent used for forming the surface layer may be any solvent as long as it can dissolve or disperse the polyfunctional radical polymerizable compound, the organic resin fine particles, and the metal oxide fine particles (or the inorganic fine particles), and examples thereof include methanol, ethanol, n-propanol, isopropanol, n-butanol, t-butanol, sec-butanol, benzyl alcohol, toluene, xylene, methylene chloride, methyl ethyl ketone, cyclohexane, ethyl acetate, butyl acetate, methyl cellosolve, ethyl cellosolve, tetrahydrofuran, and 1-bis (1-bis) butyl alcoholAlkane, 1, 3-dioxolane, pyridine, diethylamine, and the like, but are not limited thereto.
Examples of the coating method of the coating liquid for forming the surface layer include known methods such as a dip coating method, a spray coating method, a spin coating method, a bead coating method, a doctor blade coating method, an electron beam coating method, a slide hopper method, and a circular slide hopper method.
The coating liquid for forming the surface layer is preferably applied using a circular slide hopper coating apparatus.
Hereinafter, a method of applying the coating liquid for forming the surface layer using the circular slide hopper coating device will be specifically described.
As shown in fig. 2 and 3, the circular slide hopper coating apparatus is composed of a cylindrical base material 251, an annular coating head 260 provided so as to surround the periphery thereof, and a reservoir tank 254 for storing a coating liquid L.
The substrate 251 referred to herein is a substrate to which a surface layer forming coating liquid should be applied, and is, for example, a substrate in a state in which an intermediate layer and a photosensitive layer are formed on a conductive support (a substrate in which a surface layer is not formed).
A narrow coating liquid distribution slit 262 having a coating liquid outlet 261 opening on the side of the base material 251 is formed in the coating head 260 over the entire circumference of the annular coating head 260 in a direction perpendicular to the longitudinal direction of the base material 251. The coating liquid distribution slit 262 communicates with an annular coating liquid distribution chamber 263, and the coating liquid distribution chamber 263 is formed so as to be supplied with the coating liquid L in the reservoir tank 254 via a supply pipe 264 by a pressure-feed pump 255.
A sliding surface 265 inclined continuously downward and formed to have a slightly larger size than the outer size of the base 251 and a terminal end is formed below the coating liquid outlet 261 of the coating liquid distribution slit 262, and a lip (bead) 266 extending downward from the terminal end of the sliding surface 265 is formed.
In such a circular slide hopper coating apparatus, when the coating liquid L is pushed out from the coating liquid distribution slit 262 and flows down along the sliding surface 265 while the base material 251 is moved in the direction of the arrow, the coating liquid L reaching the end of the sliding surface 265 forms a bead between the end of the sliding surface 265 and the outer peripheral surface of the base material 251, and then is applied to the surface of the base material 251 to form a coating film F, and excess coating liquid L is discharged from the discharge port 267.
In the coating method using such a circular slide hopper coating apparatus, since the sliding surface end and the base material are arranged with a certain gap (about 2 μm to 2mm), the base material is not damaged, and even when layers having different properties are formed, the already-coated layers can be coated without being damaged. Further, when a plurality of layers having different properties and dissolved in the same solvent are formed, the time of existence in the solvent is shorter than that in the dip coating method, and therefore, the lower layer component is hardly eluted to the upper layer side and can be coated without being eluted to the coating bath, and thus, for example, coating can be performed without deteriorating dispersibility of the metal oxide fine particles (or inorganic fine particles) and the organic resin fine particles.
The coating film may be cured without drying, but it is preferable to perform curing after natural drying or thermal drying.
The drying conditions can be appropriately selected depending on the type of solvent, film thickness, and the like. The drying temperature is preferably between room temperature and 180 ℃, and particularly preferably between 80 and 140 ℃. The drying time is preferably 1 minute to 200 minutes, and particularly preferably 5 minutes to 100 minutes.
Examples of the method of polymerizing the radically polymerizable compound include a method of generating a reaction by electron beam cleavage, a method of adding a radical polymerization initiator and generating a reaction by light or heat, and the like. The radical polymerization initiator may be any of a photopolymerization initiator and a thermal polymerization initiator. Further, a photopolymerization initiator and a thermal polymerization initiator may be used together.
The radical polymerization initiator is preferably a photopolymerization initiator, and particularly, an alkylbenzene-based compound or a phosphine oxide-based compound is preferably used. Particularly preferred is a compound having an α -hydroxyacetophenone structure or an acylphosphine oxide structure.
Specific examples of acylphosphine oxide compounds as photopolymerization initiators are shown below.
[ chemical formula 8 ]
The polymerization initiators may be used in 1 kind alone or in combination of 2 or more kinds.
The addition ratio of the polymerization initiator is preferably 0.1 to 20 parts by mass, more preferably 0.5 to 10 parts by mass, per 100 parts by mass of the radical polymerizable compound.
As the curing treatment, a coating film is irradiated with actinic rays to generate radicals to polymerize and form cross-linking coupling by cross-linking reaction between and within molecules to cure, thereby producing a cured resin. The actinic ray is more preferably ultraviolet ray or electron beam, and ultraviolet ray is particularly preferred because it is easy to use.
The ultraviolet light source may be any light source that generates ultraviolet light, and can be used without limitation. For example, a low-pressure mercury lamp, a medium-pressure mercury lamp, a high-pressure mercury lamp, an ultrahigh-pressure mercury lamp, a carbon arc lamp, a metal halide lamp, a xenon lamp, a flash (pulse) xenon lamp, or the like can be used.
The irradiation conditions are different depending on the lamp, but the dose of actinic rays is usually 5 to 500mJ/cm2Preferably 5 to 100mJ/cm2。
The power of the lamp is preferably from 0.1kW to 5kW, particularly preferably from 0.5kW to 3 kW.
As the electron beam source, there is no particular limitation on the electron beam irradiation device, and as such an electron beam accelerator for electron beam irradiation, a device of a curtain beam (curl beam) system which is relatively inexpensive and can obtain a large output can be effectively used. Preferably, the acceleration voltage during electron beam irradiation is 100 to 300 kV. Preferably, the absorbed dose is 0.5-10 Mrad.
The irradiation time for obtaining the necessary irradiation amount of the actinic ray is preferably 0.1 second to 10 minutes, and more preferably 0.1 second to 5 minutes from the viewpoint of the operation efficiency.
In the step of forming the surface layer, drying can be performed before and after irradiation with actinic rays and while the actinic rays are being irradiated, and the timing of drying can be appropriately selected in combination.
[ toner ]
The toner used in the image forming apparatus having the photoreceptor of the present invention and the image forming method using the photoreceptor of the present invention is not particularly limited, but is preferably a toner having a true sphere of 100 and a shape factor SF of less than 140. If the shape factor SF is less than 140, good transferability and the like can be obtained, and the image quality of the obtained image can be improved. The toner particles constituting the toner preferably have a volume average particle diameter of 2 to 8 μm from the viewpoint of the desire for high image quality.
The toner particles usually contain a binder resin and a colorant, and if necessary, a release agent. The binder resin, the colorant and the release agent can be any of those conventionally used for toner, and are not particularly limited.
The method for producing the toner particles is not particularly limited, and examples thereof include a known polymerization method such as a usual pulverization method, a wet fusion spheronization method in a dispersion medium, suspension polymerization, dispersion polymerization, and emulsion polymerization aggregation method.
In addition, inorganic fine particles such as silica and titania having an average particle diameter of about 10 to 300nm and an abrasive having an average particle diameter of about 0.2 to 3 μm can be added to the toner particles in an appropriate amount as an external additive. The toner particles can be mixed with a carrier such as a ferrite bead having an average particle diameter of 25 to 45 μm to be used as a two-component developer.
[ image Forming apparatus ]
An image forming apparatus of the present invention includes: a photoreceptor; a charging mechanism for charging the surface of the photoreceptor; an exposure mechanism for forming an electrostatic latent image on the surface of the photoreceptor; a developing mechanism for developing the electrostatic latent image with toner to form a toner image; a transfer mechanism for transferring the toner image to a transfer material; a fixing mechanism for fixing the toner image transferred to the transfer member; the image forming apparatus includes a cleaning mechanism for removing residual toner on a photoreceptor, a lubricant applying mechanism for applying a lubricant to a surface of the photoreceptor, and the photoreceptor of the present invention is provided as the photoreceptor. The lubricant applying mechanism includes, for example, a solid lubricant, a brush for scraping the solid lubricant and supplying the solid lubricant to the photoreceptor, a drive source for driving the brush, and a housing for holding the solid lubricant and the brush, and is grounded in front of the cleaning blade.
Preferably, the charging mechanism is a contact or non-contact roller charging type charging mechanism.
Fig. 4 is a sectional view for explaining a configuration of an example of an image forming apparatus according to the present invention.
This image forming apparatus is called a tandem-type color image forming apparatus, and is configured by 4 sets of image forming sections (image forming units) 10Y, 10M, 10C, and 10Bk, an endless belt-shaped intermediate transfer body unit 7, a paper feed mechanism 21, and a fixing mechanism 24. A document image reading apparatus SC is disposed on an upper portion of a main body a of the image forming apparatus.
The image forming section 10Y for forming a yellow image includes a charging mechanism 2Y, an exposure mechanism 3Y, a developing mechanism 4Y, a primary transfer roller 5Y as a primary transfer mechanism, and a cleaning mechanism 6Y arranged around the drum-shaped photoreceptor 1Y. The image forming unit 10M for forming a magenta image includes a drum-shaped photoreceptor 1M, a charging mechanism 2M, an exposure mechanism 3M, a developing mechanism 4M, a primary transfer roller 5M as a primary transfer mechanism, and a cleaning mechanism 6M. The image forming section 10C for forming a cyan image includes a drum-shaped photoreceptor 1C, a charging mechanism 2C, an exposure mechanism 3C, a developing mechanism 4C, a primary transfer roller 5C as a primary transfer mechanism, and a cleaning mechanism 6C. The image forming unit 10Bk for forming a black image includes a drum-shaped photoreceptor 1Bk, a charging mechanism 2Bk, an exposure mechanism 3Bk, a developing mechanism 4Bk, a primary transfer roller 5Bk as a primary transfer mechanism, and a cleaning mechanism 6 Bk. The image forming apparatus of the present invention uses the photoreceptor of the present invention as the photoreceptors 1Y, 1M, 1C, and 1 Bk.
The 4 sets of image forming units 10Y, 10M, 10C, and 10Bk are configured by charging mechanisms 2Y, 2M, 2C, and 2Bk, exposure mechanisms 3Y, 3M, 3C, and 3Bk, rotating developing mechanisms 4Y, 4M, 4C, and 4Bk, and cleaning mechanisms 6Y, 6M, 6C, and 6Bk for cleaning the photoreceptors 1Y, 1M, 1C, and 1Bk, respectively, with the photoreceptors 1Y, 1M, 1C, and 1Bk as the center.
The image forming units 10Y, 10M, 10C, and 10Bk have the same configuration except that the toner images formed on the photoreceptors 1Y, 1M, 1C, and 1Bk are different in color, and the image forming unit 10Y will be described in detail as an example.
The image forming unit 10Y is a device in which a charging mechanism 2Y, an exposure mechanism 3Y, a developing mechanism 4Y, and a cleaning mechanism 6Y are arranged around a photoreceptor 1Y as an image forming member to form a yellow (Y) toner image on the photoreceptor 1Y. In the present embodiment, at least the photoreceptor 1Y, the charging mechanism 2Y, the developing mechanism 4Y, and the cleaning mechanism 6Y in the image forming unit 10Y are integrated.
The charging mechanism 2Y is a mechanism for applying a uniform potential to the photoreceptor 1Y. In the present invention, the charging mechanism is preferably a contact or non-contact roller charging type charging mechanism. In the application method, it is desirable to superimpose an AC bias on a DC bias from the viewpoint of image quality, but there is no problem even with only a DC bias.
The charging mechanism is a contact or non-contact charging type mechanism, which can significantly reduce the amount of ozone generated, and can achieve an effect of reducing power consumption due to a reduction in applied voltage compared to the corona charging type mechanism, thereby saving space.
The exposure mechanism 3Y is a mechanism that forms an electrostatic latent image corresponding to a yellow image by exposing the photoreceptor 1Y, to which a uniform potential is applied by the charging mechanism 2Y, based on an image signal (yellow), and as the exposure mechanism 3Y, a mechanism including LEDs and image forming elements, in which light emitting elements are arrayed in an array in the axial direction of the photoreceptor 1Y, a laser optical system, or the like can be used.
The developing mechanism 4Y is configured by, for example, a developing sleeve that holds a developer and rotates with a magnet built therein, and a voltage applying device that applies a dc and/or ac bias between the photoreceptor and the developing sleeve.
The fixing mechanism 24 is, for example, a fixing mechanism of a heat roller fixing system including a heat roller having a heat source therein and a pressure roller provided in a state of being pressed against the heat roller to form a fixing nip portion.
The cleaning mechanism 6Y is composed of a cleaning blade and a brush roller provided upstream of the cleaning blade.
Specifically, as shown in fig. 5, the cleaning mechanism 6 includes a cleaning blade 66A disposed so that the tip thereof abuts the surface of the photoreceptor 1, and a brush roller 66C disposed upstream of the cleaning blade 66A and in contact with the surface of the photoreceptor 1.
In fig. 5, reference numeral 2A denotes a charging roller, 2B denotes a cleaning roller, 9 denotes a charge removing mechanism, 44A denotes a developing roller, 44B denotes a feed screw, 44C denotes a conveyance screw, 44D denotes a regulating blade, and 66J denotes a conveyance screw.
The cleaning blade 66A has a function of removing residual toner adhering to the photoreceptor 1 and a function of wiping the surface of the photoreceptor 1.
The cleaning blade 66A is supported by a support member 66B. As a material of the cleaning blade 66A, a rubber elastomer can be used, and as a material thereof, urethane rubber, silicone rubber, fluorine-containing rubber, chloroprene rubber, butadiene rubber, and the like are known, and among these, urethane rubber is particularly preferable because it is superior in abrasion resistance compared with other rubbers.
The support member 66B is made of a plate-like metal member or plastic member. Examples of the metal member include stainless steel plate, aluminum plate, and damping steel plate.
In the present invention, it is preferable that the tip end portion of the cleaning blade 66A abutting on the surface of the photoreceptor 1 abuts in a state where a load is applied in a direction opposite to (reverse to) the rotation direction of the photoreceptor 1. As shown in fig. 5, when the tip of the cleaning blade 66A abuts against the photoreceptor 1, an abutment surface is preferably formed.
As shown in fig. 6, the contact load P and the contact angle θ of the cleaning blade 66A against the photoreceptor 1 are preferably 5 to 40N/m, and θ is preferably 5 to 35 °.
The contact load P is a vector value in the normal direction of the contact force P' when the cleaning blade 66A is brought into contact with the drum-shaped photoreceptor 1.
The contact angle θ represents an angle formed by the tangent line X at the contact point a of the photoreceptor 1 and the blade before deformation.
Reference numeral 66E denotes a rotary shaft that allows the support member 66B to rotate, and 66G denotes a load spring.
The preferred free length L is 6-15 mm.
As shown in fig. 5, the free length L of the cleaning blade 66A is a length from the position of the end B of the support member 66B to the tip end point of the cleaning blade 66A before deformation.
The thickness t of the cleaning blade 66A is preferably 0.5 to 10 mm.
Here, as shown in fig. 5, the thickness t of the cleaning blade 66A is a length in a direction perpendicular to the adhesive surface of the support member 66B.
The brush roller 66C has a function of removing the residual toner adhering to the photoreceptor 1, collecting the residual toner removed by the cleaning blade 66A, and a function of wiping the surface of the photoreceptor 1. That is, the brush roller 66C contacts the surface of the photoreceptor 1, and rotates in the same direction as the direction in which the photoreceptor 1 travels at the contact portion, thereby removing residual toner and paper dust on the photoreceptor 1, and also conveys the residual toner removed by the cleaning blade 66A and collects the toner on the conveyor screw 66J. Then, the surface of the photoreceptor 1 is scraped off and recovered.
It is preferable to remove the removed matter such as the residual toner transferred from the photoconductor 1 to the brush roller 66C by bringing a flicker element (flicker)66I as a removing mechanism into contact with the brush roller 66C. Then, the toner adhering to the flicker element 66I is removed by a blade 66D, and the toner is collected into the conveyance screw 66J. The collected toner is taken out to the outside as waste, or is transported to the developing device via a recycling pipe (not shown) for toner recycling and reused.
Preferably, a metal tube made of stainless steel, aluminum, or the like is used as the scintillator 66I.
The doctor blade 66D is preferably brought into contact with the scintillator element 66I so that the tip thereof forms an acute angle with respect to the rotation direction of the scintillator element 66I, using an elastic plate such as a phosphor bronze plate, a polyethylene terephthalate plate, or a polycarbonate plate.
The cleaning mechanism 6 includes a lubricant applying mechanism for applying a lubricant to the surface of the photoreceptor 1.
Specifically, as shown in fig. 6, a solid material 66K of the lubricant pressed to the brush roller 66C by the load spring 66S is provided, and the solid material 66K is rubbed by the rotation of the brush roller 66C to apply the lubricant to the surface of the photoconductor 1.
As the lubricant, for example, zinc stearate or the like can be used.
As the brush roller 66C, a conductive or semiconductive brush roller may be used. As a brush constituting material of the brush roller 66C, any material can be used, and a hydrophobic fiber-forming polymer having a high dielectric constant is preferably used. Examples of such a polymer include rayon, nylon, polycarbonate, polyester, methacrylic resin, acrylic resin, polyvinyl chloride, polyvinylidene chloride, polypropylene, polystyrene, polyvinyl acetate, a styrene-butadiene copolymer, a vinylidene chloride-acrylonitrile copolymer, a vinyl chloride-vinyl acetate-maleic anhydride copolymer, a silicone resin, a silicone-alkyd resin, a phenol-formaldehyde resin, a styrene-alkyd resin, and polyvinyl acetal (e.g., polyvinyl butyral). These resins can be used alone or as a mixture of 2 or more. Particularly preferred are rayon, nylon, polyester, acrylic, polypropylene.
The brush roller 66C may be a conductive or semiconductive brush roller, and a brush roller containing a low-resistance substance such as carbon as a constituent material and adjusted to have an arbitrary resistivity may be used.
The thickness of 1 bristle used for the brush roller 66C is preferably 5 to 20 denier. The thickness of the brush bristles is preferably 5 to 20 denier because sufficient wiping force for reliably removing the adhering substances from the surface of the photoreceptor 1 is given, and there is no possibility of causing damage to the surface of the photoreceptor 1 or progressing abrasion.
"denier" means a value obtained by measuring the mass of 9000m in g (grams) of the length of bristles (fibers) constituting the brush roller 66C.
The brush roller 66C has a bristle density of 4.5X 102/cm2～2.0×104/cm2(number of bristles per square centimeter).
If the bristle density is less than 4.5X 102/cm2The rigidity is low, the rubbing force is weak, the rubbing may be uneven, and the adhered matter cannot be removed uniformly. If it is larger than 2.0X 104/cm2The image becomes rigid and the rubbing force becomes strong, so that the photoreceptor 1 is excessively worn, and a defective image such as fog due to a decrease in sensitivity or a black line due to a scratch is generated.
Preferably, the entrance amount (entrance amount) of the brush roller 66C into the photoreceptor 1 is set to 0.4 to 1.5 mm.
The entry amount is a load applied to the brush roller 66C by the relative movement between the photoreceptor 1 drum and the brush roller 66C. The load corresponds to the wiping force received from the brush roller 66C when viewed from the photoreceptor 1 drum, and defining the range means that the photoreceptor 1 needs to be wiped with an appropriate force.
The entry amount is an entry length of the brush bristles into the photoreceptor 1 when the brush roller 66C is brought into contact with the photoreceptor 1, and the brush bristles are linearly entered into the photoreceptor 1 without being bent on the surface thereof.
As the core material of the roller portion used in the brush roller 66C, metal such as stainless steel or aluminum, paper, plastic, or the like is mainly used, but not limited thereto.
It is preferable that the brush roller 66C is rotated in such a manner that its abutting portion moves in the same direction as the surface of the photoreceptor 1. If the contact portion moves in the opposite direction, if an excessive amount of toner is present on the surface of the photoreceptor 1, the toner removed by the brush roller 66C may overflow and contaminate the recording paper or the device.
Preferably, the surface speed ratio of the photoreceptor 1 and the brush roller 66C is in the range of 1 to 1.1 to 1 to 2 when they move in the same direction.
In the image forming apparatus of the present invention, it is preferable that the components such as the photoreceptor, the developing mechanism, and the cleaning mechanism are integrally combined as a process cartridge (image forming unit), and the image forming unit may be detachably attached to the apparatus main body. Further, at least one of the charging mechanism, the exposure mechanism, the developing mechanism, the transfer mechanism, and the cleaning mechanism may be supported integrally with the photoreceptor to form a process cartridge (image forming unit), and the process cartridge may be configured to be detachable as a single image forming unit detachable from the apparatus main body by using a guide mechanism such as a guide rail of the apparatus main body.
The endless belt-shaped intermediate transfer body unit 7 includes an endless belt-shaped intermediate transfer body 70 as a second image bearing member, which is wound around a plurality of rollers and is rotatably supported in a semiconductive endless belt shape.
The images of the respective colors formed by the image forming units 10Y, 10M, 10C, and 10Bk are sequentially transferred onto the rotating endless intermediate transfer body 70 by the primary transfer rollers 5Y, 5M, 5C, and 5Bk as primary transfer means, and a synthesized color image is formed. A transfer material (an image support body carrying a final image after fixing, for example, plain paper, a transparent sheet, or the like) P accommodated in the paper feed cassette 20 is supplied from a supply mechanism 21, conveyed to a secondary transfer roller 5B as a secondary transfer mechanism via a plurality of intermediate rollers 22A, 22B, 22C, and 22D and a registration roller 23, and secondarily transferred onto the transfer material P to collectively transfer a color image. The transfer material P to which the color image is transferred is subjected to fixing processing by the fixing mechanism 24, and is sandwiched by the discharge rollers 25 and placed on the paper discharge tray 26 outside the machine. Here, the transfer support for the toner image formed on the photoreceptor such as the intermediate transfer member or the transfer material is collectively referred to as a transfer medium.
On the other hand, after the color image is transferred to the transfer material P by the secondary transfer roller 5b as a secondary transfer mechanism, the endless belt-shaped intermediate transfer body 70 having undergone bending separation of the transfer material P is cleaned of residual toner by the cleaning mechanism 6 b.
In the image forming process, the primary transfer roller 5Bk is always in contact with the photoconductor 1 Bk. The other primary transfer rollers 5Y, 5M, and 5C are in contact with the corresponding photoreceptors 1Y, 1M, and 1C only during color image formation.
The secondary transfer roller 5b is in contact with the endless intermediate transfer body 70 only when the transfer material P passes therethrough to perform secondary transfer.
Further, the housing 8 can be extracted from the apparatus main body a via the support rails 82L, 82R.
The frame 8 is composed of the image forming units 10Y, 10M, 10C, and 10Bk and the endless intermediate transfer unit 7.
The image forming units 10Y, 10M, 10C, and 10Bk are arranged in a vertical row. An endless intermediate transfer unit 7 is disposed on the left side of the photoreceptors 1Y, 1M, 1C, and 1Bk in the figure. The endless intermediate transfer body unit 7 includes an endless intermediate transfer body 70 rotatable by winding rollers 71, 72, 73, and 74, primary transfer rollers 5Y, 5M, 5C, and 5Bk, and a cleaning mechanism 6 b.
The image forming apparatus shown in fig. 4 shows a color laser printer, but the present invention is also applicable to a monochromatic laser printer and a copying machine. In addition, a light source other than a laser, for example, an LED light source may be used as the exposure light source.
According to the image forming apparatus as described above, since the photoreceptor of the present invention is provided, it is possible to obtain excellent cleaning performance, and therefore, it is possible to form a high-quality image for a long period of time, and even when the supply unevenness of the lubricant occurs, it is possible to suppress the occurrence of the image density unevenness associated therewith.
[ image Forming method ]
An image forming method of the present invention includes: a charging step of charging the surface of the photoreceptor; an exposure step of forming an electrostatic latent image on the surface of the photoreceptor; a developing step of developing the electrostatic latent image with a toner to form a toner image; a transfer step of transferring the toner image to a transfer material; a fixing step of fixing the toner image transferred to the transfer member; and a cleaning step of removing residual toner on the photoreceptor, wherein the photoreceptor of the present invention is used as the photoreceptor, and the developer contains a lubricant. In the charging step, it is preferable to perform charging by a contact or non-contact roller charging method.
The image forming method of the present invention can be performed using, for example, the image forming apparatus shown in fig. 4. In the image forming method of the present invention, the image forming apparatus may be provided with a lubricant applying mechanism or may use a developer containing a lubricant as the developer. In the case where the developer contains a lubricant, the lubricant is supplied to the surface of the photoreceptor by a developing electric field in the developing step.
The lubricant is not particularly limited as long as it has lubricity and cracking property, and for example, zinc stearate or the like can be used. The number average primary particle diameter of the lubricant is preferably 1 to 20 μm, for example. The lubricant is preferably contained in the developer in a proportion of 0.01 to 0.3 mass% so as not to affect the chargeability of the toner.
In the above-described image forming method, since the photoreceptor of the present invention can be used to obtain good cleanability, it is possible to form a high-quality image for a long period of time, and even when the supply unevenness of the lubricant occurs, it is possible to suppress the occurrence of the image density unevenness associated therewith.
[ examples ] A method for producing a compound
The present invention will be described in detail below with reference to examples, but the present invention is not limited to the following examples. In the following, "parts" means "parts by mass".
EXAMPLE 1
[ production example 1 of photoreceptor ]
A conductive support (1) having a surface roughened finely is prepared by cutting the surface of a cylindrical aluminum body having a diameter of 60 mm.
(formation of intermediate layer)
A dispersion having the following composition was diluted twice with the same solvent as described below, and the resulting solution was allowed to stand overnight and then filtered (filter; Ridi mesh5 μm filter manufactured by Poulter, Japan) to prepare a coating liquid [ 1 ].
Binder resin: polyamide resin "CM 8000" (manufactured by Toray corporation) 1 part
Metal oxide particles: titanium oxide SMT500SAS (manufactured by Nippon Imperial chemical Co., Ltd.) 3 parts
Solvent: 10 portions of methanol
The dispersion was carried out in a batch system for 10 hours using a sand mill as a disperser.
The intermediate layer [ 1 ] was formed on the conductive support [ 1 ] by dip coating using the intermediate layer-forming coating liquid [ 1 ], and the dry film thickness was 2 μm.
(formation of Charge generating layer)
Charging a charge generating substance: 20 parts of the following pigment (CG-1), adhesive resin: polyvinyl butyral resin "# 6000-C" (manufactured by electrochemical engineering Co., Ltd.) 10 parts, solvent: 700 parts of tert-butyl acetate, solvent: 300 parts of 4-methoxy-4-methyl-2-pentanone were mixed and dispersed for 10 hours by a sand mill to prepare a charge generation layer formation coating liquid [ 1 ]. The charge generation layer formation coating liquid [ 1 ] was applied onto the intermediate layer [ 1 ] by a dip coating method to form a charge generation layer [ 1 ] having a dry film thickness of 0.3 μm.
< Synthesis of pigment (CG-1) >
(1) Synthesis of amorphous titanyl phthalocyanine
29.2 parts of 1, 3-diiminoisoindoline (diimimosoindoline) was dispersed in 200 parts of o-dichlorobenzene, 20.4 parts of titanium tetra-n-butoxide was added thereto, and the mixture was heated at 150 to 160 ℃ for 5 hours under a nitrogen atmosphere. After cooling, the precipitated crystal was filtered, washed with chloroform, washed with a 2% hydrochloric acid aqueous solution, washed with water and methanol, and dried to obtain 26.2 parts (yield 91%) of crude oxytitanium phthalocyanine.
Next, the crude titanyl phthalocyanine was dissolved in 250 parts of concentrated sulfuric acid at 5 ℃ or lower while stirring for 1 hour, and then poured into 5000 parts of 20 ℃ water. The precipitated crystals were filtered and sufficiently washed with water to obtain 225 parts of a wet paste product.
The wet paste was frozen in a freezer, thawed again, and then filtered and dried to obtain 24.8 parts (yield 86%) of amorphous titanyl phthalocyanine.
(2) Synthesis of (2R, 3R) -2, 3-butanediol adduct titanyl phthalocyanine (CG-1)
10.0 parts of the amorphous titanyl phthalocyanine and 0.94 part (0.6 equivalent ratio) of (2R, 3R) -2, 3-butanediol (equivalent ratio is equivalent ratio to titanyl phthalocyanine, the same applies hereinafter) are mixed with 200 parts of o-dichlorobenzene (ODB), and the mixture is heated and stirred at 60 to 70 ℃ for 6.0 hours. After standing overnight, crystals produced by adding methanol to the reaction solution were filtered, and the filtered crystals were washed with methanol to obtain (a pigment containing (2R, 3R) -2, 3-butanediol adduct oxytitanium phthalocyanine) CG-1: 10.3 parts. In the X-ray diffraction spectrum of the pigment (CG-1), there are clear peaks at 8.3 DEG, 24.7 DEG, 25.1 DEG, and 26.5 deg. In the mass spectrum, there are peaks at 576 and 648, in the IR spectrum at 970cm-1Nearby Ti ═ O, 630cm-1Double absorption of O-Ti-O occurs nearby. In addition, in thermal analysis (TG), since there was a mass loss of about 7% at 390 to 410 ℃, it was estimated that the molecular weight of titanyl phthalocyanine and (2R, 3R) -2, 3-butanediol was 1: 1 mixture of adduct and non-adduct (non-adduct) titanyl phthalocyanine.
The BET relative surface area of the obtained pigment (CG-1) measured by a flow type automatic measuring apparatus (Micrometrics flowsaw type: Shimadzu corporation) was 31.2m2/g。
(formation of Charge transport layer)
Charging a charge transport material: 225 parts of the following compound A, adhesive resin: polycarbonate resin "Z300" (manufactured by mitsubishi gas chemical corporation) 300 parts, antioxidant: 6 parts of Irganox1010 (manufactured by Ciba-Geigy, Japan), solvent: 1600 parts of THF (tetrahydrofuran), solvent: a coating liquid [ 1 ] for forming a charge transport layer was prepared by mixing and dissolving 400 parts of toluene and 1 part of silicone oil "KF-50" (manufactured by shin-Etsu chemical Co., Ltd.).
A charge transport layer [ 1 ] having a dry film thickness of 20 μm was formed by applying a charge transport layer forming coating liquid [ 1 ] onto the charge generation layer [ 1 ] using a circular slide hopper coating apparatus.
[ chemical formula 9 ]
(formation of surface layer)
(1) Production of Metal oxide microparticles
A mixed solution of 100 parts of tin oxide (number-average primary particle diameter: 20nm), 30 parts of a compound (S-13) exemplified as a surface treatment agent, 300 parts of a mixed solvent of toluene/isopropyl alcohol 1/1 (mass ratio), and zirconia beads was added to a sand mill and stirred at about 40 ℃ at a rotation speed of 1500rpm, and the treated mixture was taken out, put into a henschel mixer and stirred at a rotation speed of 1500rpm for 15 minutes, and then dried at 120 ℃ for 3 hours, thereby completing the surface treatment of tin oxide based on the compound having a radical polymerizable functional group, and tin oxide having a surface treated was obtained. This was used as metal oxide fine particles [ 1 ]. The surface of the tin oxide particles was covered with the exemplified compound (S-13) by the surface treatment with the compound having a radical polymerizable functional group described above.
(2) Formation of a surface layer
150 parts of metal oxide fine particles [ 1 ], a polyfunctional radical polymerizable organic compound: 100 parts of the above exemplified compound (M1), charge transporting compound: 20 parts of the above exemplified compound (CTM-10) were mixed under light shielding, and the solvent: 400 parts of 2-butanol, solvent: after 20 parts of tetrahydrofuran was mixed and stirred and dispersed for 5 hours using a sand mill as a dispersing machine, a polymerization initiator: 12.5 parts of Irgacure 819 (manufactured by BASF Japan) and 10 parts of EPOSTARS (manufactured by Japan catalyst) were mixed and stirred for 1 hour to prepare a coating liquid [ 1 ] for forming a surface layer. The surface layer-forming coating liquid [ 1 ] was applied to the charge transport layer [ 1 ] using a circular slide hopper coating apparatus to form a coating film, and ultraviolet light was irradiated for 1 minute using a metal halide lamp to form a surface layer [ 1 ] having a dry film thickness of 2.5 μm, thereby producing a photoreceptor [ 1 ].
[ production examples 2 to 9 of photoreceptor ]
Photoreceptors [ 2 ] to [ 9 ] were produced in the same manner as in table 1 except that the type and the amount of the organic resin fine particles used were changed in the formation of the surface layer in production example 1 of the photoreceptor.
[ production example 10 of photoreceptor ]
A photoreceptor was produced in the same manner as in production example 1 except that no charge transporting compound was added to form the surface layer [ 10 ].
[ production example 11 of photoreceptor ]
In the formation of the surface layer in production example 1 of the photoreceptor, a photoreceptor [ 11 ] was produced in the same manner except that the organic resin fine particles were not added.
[ production example 12 of photoreceptor ]
In the formation of the surface layer in production example 1 of the photoreceptor, a photoreceptor was produced in the same manner as in [ 12 ] except that the metal oxide fine particles were not added.
[ examples 1 to 10, comparative examples 1 to 2 ]
The photoreceptors [ 1 ] to [ 12 ] obtained as described above were evaluated for cleanability, image density unevenness, and abrasion resistance as shown below.
(1) Evaluation of cleaning Properties
The cleanability is determined by visual observation whether or not the toner band developed on the photoreceptor is wiped by the blade with the external driving machine.
Specifically, a modified image forming unit using "bizhubProC 6500" (manufactured by konica minolta) was placed on an external drive machine. At this time, the image forming unit uses a product of the end of endurance. As shown in fig. 5, the image forming unit is constituted by a photoreceptor (1), a charging mechanism (2), a developing mechanism (4), a cleaning mechanism (cleaning blade) (6), and a casing. The developing mechanism (4) is of a two-component developing type and is constituted by a developing roller (44A) (constituted by a magnet roller and a developing sleeve), a regulating blade (44D), supply/conveyance screws (44B, 44C), and a casing. The external driving machine can drive the photoreceptor and the developing roller and apply a predetermined developing bias to the developing roller.
The evaluation method is as follows.
(1) An image forming unit is provided to the external driving machine.
(2) A high-voltage power supply output line was connected to a developing mechanism (developing roller), and a developing bias was adjusted so that the amount of toner on the photoreceptor became 2g/m by DC development2. At this time, in order to prevent the toner concentration in the developer from decreasing, it is necessary to replenish the toner in a necessary amount at a proper time.
(3) After the image forming unit was directly driven for 5 seconds, the developing bias was applied for 0.5 seconds, and then stopped after rotating for 0.3 seconds.
(4) The degree of the toner wiping residue on the photoreceptor was evaluated according to the following evaluation criteria.
Evaluation criteria-
O: no wiping residue
And (delta): with strip-like wiping residues
X: the wiping residue is generated in a planar form
(2) Evaluation of image Density unevenness
In the actual machine, 10 images a4 of half-full black and half-full white as shown in fig. 7A were printed, and then the difference in image density between the full black history section and the full white history section in the halftone image output shown in fig. 7B was evaluated based on the following evaluation criteria. The image density was measured by "TD-904" manufactured by Mibech corporation.
Evaluation criteria-
O: the concentration difference is less than 0.02
And (delta): the concentration difference is more than 0.02 and less than 0.03
X: the concentration difference is more than 0.03
(3) Evaluation of abrasion resistance
After outputting 100k sheets of a character table having a print rate of 5% in a real machine, the amount of wear of the surface layer was measured by a measuring instrument "FISCHERSCOPE (registered trademark) MMS (registered trademark) PC" manufactured by fisher corporation to evaluate the wear. The deterioration amount of the surface layer was ∈ when it was less than 0.6 μm, ∈ when it was 0.6 μm or more and less than 1.2 μm, and × when it was 1.2 μm or more.
EXAMPLE 2
[ production example 21 of photoreceptor ]
The same conductive support as in "photoreceptor manufacturing example 1" above was used. Further, "formation of intermediate layer", "formation of charge generation layer" and "formation of charge transport layer" were formed in the same manner as in "production example 1 of photoreceptor" described above, and an intermediate layer [ 21 ], a charge generation layer [ 21 ] and a charge transport layer [ 21 ] were obtained.
(formation of surface layer)
(1) Preparation of organic resin Fine particles subjected to surface treatment
2g of water was added to 20g of methanol, and the mixture was stirred. Adding concentrated hydrochloric acid into the mixture to adjust the pH value to 2-3. To this solution was added 2.5g of the above exemplified compound (C-5) as a silane coupling agent, and the mixture was stirred at room temperature for 1 hour. Next, a methanol dispersion of melamine resin "EPOSSTARS 6" (average particle diameter: 400nm, manufactured by Japan catalyst Co., Ltd.) having a concentration of 10% by mass was added and stirred at 40 ℃ for 2 hours. After the completion of the heating and stirring, a saturated aqueous sodium hydrogencarbonate solution was poured for neutralization. After neutralization, filtration and drying at 120 ℃ for 2 hours were carried out to carry out surface treatment. The resulting fine particles were used as organic resin fine particles [ 21 ].
(2) Formation of a surface layer
Mixing inorganic fine particles [ 21 ]: 85 parts of tin oxide (average particle diameter: 20nm), 25 parts of organic resin fine particles [ 21 ], a polyfunctional radical polymerizable compound: 100 parts of the above exemplified compound (M1), solvent: 400 parts of 2-butanol, solvent: THF (tetrahydrofuran) 40 portions were mixed under light shielding, and after 5 hours of dispersion using a sand mill as a dispersion machine, a polymerization initiator: 10 parts of the above exemplified compound (P2) was dissolved by stirring in the absence of light to prepare a coating liquid [ 21 ]. The surface layer-forming coating liquid [ 21 ] was applied to the charge transport layer [ 21 ] by using a circular slide hopper coating apparatus to form a coating film, and ultraviolet light was irradiated for 1 minute by using a metal halide lamp to form a surface layer [ 21 ] having a dry film thickness of 5.0 μm, thereby obtaining a photoreceptor [ 21 ]. The number average primary particle diameter of the inorganic fine particles in the surface layer [ 21 ] was 20nm, and the number average primary particle diameter of the organic resin fine particles was 400 nm.
[ production examples 22 to 28 of photoreceptor ]
Photoreceptors [ 22 ] to [ 28 ] were produced in the same manner as in Table 3 except that the types of the inorganic fine particles and the organic resin fine particles used in the formation of the surface layer in production example 21 of the photoreceptor were changed.
In table 3, the inorganic fine particles [ 23 ], [ 24 ], [ 26 ], [ 27 ] are core-shell structured composite fine particles, and are obtained by the following production method.
In table 3, the organic resin fine particles [ 22 ] to [ 27 ] were obtained by the following production methods. The organic resin fine particles [ 28 ] were not subjected to surface treatment, but fine particles of melamine resin "EPASTAR S6" (manufactured by Nippon catalyst Co., Ltd.) were used as they were.
< preparation of inorganic Fine particles (23) >
To 3L of pure water, 0.1L of 35% hydrochloric acid was added and the mixture was warmed to 75 ℃. 300g of alumina core material having an average particle diameter of 200nm was suspended in the hydrochloric acid acidic solution, and to this solution was quantitatively added 36g per hour of an aqueous titanium tetrachloride solution (50 mass% as Ti) while stirring, and further added 360ml per 1 hour of caustic soda dissolved to 10 mass%. The obtained slurry containing the particles was repulped and washed until the conductivity became 100. mu.S/cm or less, and then suction-filtered to obtain a cake (cake), which was then vacuum-dried at 150 ℃ to obtain inorganic fine particles [ 23 ] in which titanium oxide was attached to the surface of the alumina core material.
< preparation of inorganic Fine particles (24) >
Inorganic fine particles [ 24 ] in which tin oxide was attached to the surface of a barium sulfate core material were produced using the production apparatus shown in FIG. 8.
Specifically, 3500cm of pure water is put into the mother liquid tank (11)3Then, 900g of spherical barium sulfate core material having an average particle diameter of 100nm was charged and circulated through 5 passes. The flow velocity of the slurry flowing out of the mother liquor tank (11) is 2280cm3And/min. The stirring speed of the strong dispersing device (13) was 16000 rpm. Diluting the slurry after the circulation in pure water to total 9000cm31600g of sodium stannate and 2.3cm of sodium stannate were added3And circulating the aqueous solution of sodium hydroxide (concentration 25N) through 5 paths. Thus, a mother liquor was obtained. While the flow rate (S1) of the mother liquor flowing out from the mother liquor tank (11) is set at 200cm3While circulating, 20% sulfuric acid was supplied to a homogenizer "magic LAB" (manufactured by IKA Japan K.K.) as a strong dispersion device (13). The feeding speed (S3) was set to 9.2cm3And/min. The volume of the homogenizer is 20cm3The stirring speed was 16000 rpm. A 15 minute cycle was performed during which sulfuric acid was continuously supplied to the homogenizer. In this way, particles were obtained in which a coating layer of tin oxide was formed on the surface of the barium sulfate core material.
The obtained slurry containing the particles was repulped and washed until the conductivity thereof became 600. mu.S/cm or less, and then suction-filtered to obtain a cake. The filter cake was dried at 150 ℃ for 10 hours in the atmosphere. Next, the dried cake was pulverized to 1 vol% H2/N2The resultant was reduction-fired at 450 ℃ for 45 minutes under an atmosphere. Thus, inorganic fine particles [ 24 ] were obtained in which tin oxide was attached to the surface of the barium sulfate core material.
In the manufacturing apparatus shown in fig. 8, reference numerals 12 and 14 denote circulation pipes forming a circulation path between the mother liquid tank 11 and the strong dispersion device 13, reference numerals 15 and 16 denote pumps provided in the circulation pipes 12 and 14, reference numeral 11a denotes an agitation blade, reference numeral 13a denotes an agitation portion, reference numerals 11b and 13b denote shafts, and reference numerals 11c and 13c denote motors.
Production of < inorganic Fine particles (26) >
In the production of the inorganic fine particles [ 23 ], inorganic fine particles [ 26 ] in which titanium oxide was attached to the surface of a silica core material were obtained in the same manner as in the case where the alumina core material was changed to a silicon core material having an average particle diameter of 250 nm.
< preparation of inorganic Fine particles (27) >
In the production of the inorganic fine particles [ 24 ], inorganic fine particles [ 27 ] in which tin oxide was attached to the surface of an alumina core material were obtained in the same manner except that the barium sulfate core material was changed to an alumina core material having an average particle diameter of 100 nm.
< preparation of organic resin Fine particles [ 22 ] to [ 27 ]
In the production of the organic resin fine particles subjected to the surface treatment in production example 21 of the photoreceptor, organic resin fine particles [ 22 ] to [ 27 ] were produced in the same manner except that the kind of the melamine resin and the kind of the coupling agent used were changed from table 3.
The obtained organic resin fine particles [ 21 ] to [ 28 ] were evaluated for flocculation property.
Specifically, 0.2g of organic resin fine particles [ 21 ] to [ 28 ] were added to 4.8g of a 2-butanol dispersion containing 20 mass% tin oxide, respectively, and the degree of aggregation was visually observed. Evaluation was performed according to the following evaluation criteria. The results are shown in Table 4.
Evaluation criteria-
Very good: no agglutination was seen at all (good)
O: the agglutination was confirmed to be slight (practically no problem)
X: agglutination was confirmed clearly (practically problematic)
[ examples 21 to 27, comparative example 3 ]
Photoreceptors [ 21 ] to [ 28 ] were mounted on an evaluation machine "bizhub PRO C6501" (manufactured by konica minolta) having basically the same configuration as that of the image forming apparatus shown in fig. 4, and evaluation was performed. Here, examples of evaluation using the photoreceptors [ 21 ] to [ 27 ] are examples 21 to 27, and an example of evaluation using the photoreceptor [ 28 ] is comparative example 3. As an exposure light source of the evaluation machine "bizhub PRO C6501", a semiconductor laser having a wavelength of 780nm was used.
Under a high-temperature and high-humidity environment at a temperature of 30 ℃ and a humidity of 85%, an endurance test was conducted in which 300000 double-sided continuous prints were made by transversely feeding a character image having an image ratio of 6% at a4, and the following evaluations of potential stability, cleanability, and scratch resistance were conducted. The results are shown in Table 4.
(1) Evaluation of potential stability
Evaluation was made based on the magnitude of potential variation in the exposed portion potential before and after the endurance test.
Specifically, the initial charging potential was adjusted to 600 ± 50V, and the amount of change (Δ V) in the exposed portion potential before and after the endurance test was calculated. Evaluation was performed according to the following evaluation criteria.
Evaluation criteria-
Very good: Δ V less than 30V (very good)
O: Δ V is 30V or more and less than 60V (good)
And (delta): Δ V is 60V or more and less than 100V (practically, there is no problem)
X: Δ V of 100V or more (problematic in practice)
(2) Evaluation of cleaning Properties
The cleanability after the durability test was evaluated according to the following evaluation criteria.
The criteria for determination are as follows.
Evaluation criteria-
Very good: no toner leakage, blade wear width less than 20 μm (good)
O: no toner residue leakage, and a blade wear width of 20 μm or more (practically no problem)
X: toner leakage (practically problematic)
(3) Scratch resistance
After the brush resistance test, halftone images were drawn on the entire surface of a3 paper, and the paper was evaluated according to the following evaluation criteria.
Evaluation criteria-
Very good: no noticeable scratches were visually observed on the photoreceptor surface, and no image defects (good) corresponding to the photoreceptor scratches were found in the halftone image
O: although slight scratches were observed on the photoreceptor surface by visual observation, no image defects were found in the halftone images corresponding to the photoreceptor scratches (no practical problem)
X: the occurrence of a scratch was clearly observed visually on the surface of the photoreceptor, and the occurrence of an image failure corresponding to the scratch was also observed in a halftone image (practically problematic)
From the results shown in table 4, it was confirmed that in examples 21 to 27 according to the present invention, the organic resin fine particles were surface-treated with the coupling agent to obtain good dispersibility, and that the organic resin fine particles had good cleaning properties while ensuring potential stability and also had high scratch resistance.
In comparative example 3, since the organic resin fine particles were not surface-treated with a coupling agent, it was confirmed that good dispersibility could not be obtained and that no cleanability and scratch resistance could be obtained. This is considered to be due to the presence of organic resin fine particles as aggregates in the surface layer. Since the aggregates are not uniformly present in the surface layer, the aggregates are easily detached from the surface layer by friction, which causes scratches. Further, it is considered that the surface state is rough due to scratches entering the surface layer, and the cleaning property is deteriorated.
Description of reference numerals: 1. 1Y, 1M, 1C, 1Bk … photoreceptors; 2. 2Y, 2M, 2C, 2Bk … charging mechanisms; 2a … charged roller; 2B … cleaning roller; 3. 3Y, 3M, 3C, 3Bk … exposure mechanism; 4. 4Y, 4M, 4C, 4Bk … developing mechanism; 5Y, 5M, 5C, 5Bk … primary transfer rollers; 5b … Secondary transfer roller; 6. 6Y, 6M, 6C, 6Bk, 6b … cleaning mechanism; 7 … intermediate transfer body unit; 8 … a frame body; 9 … static elimination mechanism; 10. 10Y, 10M, 10C, 10Bk … image forming units; 11 … mother liquor tank; 11a … stirring blade; 11b … axis; 11c … motor; 12 … circulation piping; 13 … strong dispersing device; 13a … stirring part; 13b … axis; 13c … motor; 14 … circulation piping; 15 … pump; a 16 … pump; 21 … paper supply mechanism; 20 … supply cartons; 22A, 22B, 22C, 22D … intermediate rollers; 23 … registration rollers; 24 … fixing mechanism; 25 … paper discharge rollers; 26 … paper discharge tray; 44A … developer roller; 44B … feed screw; 44C … conveyor screw; 44D … restraining squeegees; 66A … cleaning blade; 66B … support member; 66C … brush rolls; 66D … doctor blade; 66E … rotating shaft; 66G … load spring; 66I … scintillation elements; a 66J … conveyor screw; 66S … load the spring; 66K … solid material; 70 … endless belt-shaped intermediate transfer body; 71. 72, 73, 74 … rollers; 82L, 82R … support rails; a P … transfer; 101 … conductive support; 102 … a photosensitive layer; 103 … intermediate layer; 104 … charge generation layer; 105 … charge transport layer; 106 … surface layer; 107a … organic resin fine particles; 107b … fine metal oxide particles and inorganic fine particles; 251 … a substrate; 254 … storage tank; 255 … pressure-feed pump; 260 … applicator head; 261 … coating the liquid flow outlet; 262 … coating liquid dispensing slit; 263 … coating solution dispensing chamber; 264 … supply tube; 265 sliding surface 265 …; 266 … lips; 267 … discharge port; l … coating liquid; f … coating film.

Claims (20)

1. An electrophotographic photoreceptor in which a photosensitive layer is formed on a conductive support and a surface layer is formed on the photosensitive layer,
the surface layer is a surface layer obtained by containing organic resin fine particles and metal oxide fine particles in a cured resin obtained by polymerizing a compound having two or more radical polymerizable functional groups,
the organic resin fine particles are composed of a resin containing a structural unit derived from at least one of melamine and benzoguanamine, and have a number average primary particle diameter of 0.01 to 3.00 [ mu ] m,
the surface layer contains a charge transporting compound,
the charge transporting compound is represented by the following general formula (1),
wherein R is1And R2Each independently is a hydrogen atom or a methyl group, R3Is a linear or branched alkyl group having 1 to 5 carbon atoms,
the organic resin fine particles are surface-treated with a coupling agent.
2. The electrophotographic photoreceptor according to claim 1,
the organic resin fine particles are composed of a polycondensate of melamine and formaldehyde.
3. The electrophotographic photoreceptor according to claim 1,
the organic resin fine particles are contained in a proportion of 5 to 40 parts by mass relative to 100 parts by mass of the cured resin.
4. The electrophotographic photoreceptor according to claim 1,
the metal oxide fine particles are surface-treated with a surface treatment agent comprising a compound having a radical polymerizable functional group.
5. The electrophotographic photoreceptor according to claim 1,
the cured resin is an acrylic resin.
6. An image forming apparatus is characterized by comprising:
an electrophotographic photoreceptor, a charging mechanism for charging the surface of the electrophotographic photoreceptor, an exposure mechanism for forming an electrostatic latent image on the surface of the electrophotographic photoreceptor, a developing mechanism for developing the electrostatic latent image with a developer containing a toner to form a toner image, a transfer mechanism for transferring the toner image to a transfer material, a fixing mechanism for fixing the toner image transferred to the transfer material, and a cleaning mechanism for removing residual toner on the electrophotographic photoreceptor,
the image forming apparatus includes a lubricant applying mechanism for applying a lubricant to a surface of the electrophotographic photoreceptor,
the electrophotographic photoreceptor described in any one of claims 1 to 5.
7. The image forming apparatus according to claim 6,
the charging mechanism is a contact or non-contact roller charging type charging mechanism.
8. An image forming method is characterized by comprising:
a charging step of charging the surface of the electrophotographic photoreceptor, an exposure step of forming an electrostatic latent image on the surface of the electrophotographic photoreceptor, a developing step of developing the electrostatic latent image with a developer containing a toner to form a toner image, a transfer step of transferring the toner image to a transfer member, a fixing step of fixing the toner image transferred to the transfer member, and a cleaning step of removing residual toner on the electrophotographic photoreceptor,
the developer includes a lubricant that is capable of,
the electrophotographic photoreceptor according to any one of claims 1 to 5 is used as the electrophotographic photoreceptor.
9. The image forming method according to claim 8,
the charging step is performed by a contact or non-contact roller charging method.
10. An electrophotographic photoreceptor in which a photosensitive layer is formed on a conductive support and a surface layer is formed on the photosensitive layer,
the surface layer is a surface layer which is obtained by polymerizing a compound having two or more radical polymerizable functional groups, and which contains inorganic fine particles at least a part of the surface of which is formed of a metal oxide and organic resin fine particles composed of a resin containing a constituent unit derived from at least one of melamine and benzoguanamine,
the organic resin fine particles are surface-treated with a coupling agent.
11. The electrophotographic photoreceptor according to claim 10,
the organic resin fine particles have a number average primary particle diameter of 100nm to 1500 nm.
12. The electrophotographic photoreceptor according to claim 10,
the coupling agent is a coupling agent containing at least fluorine element.
13. The electrophotographic photoreceptor according to claim 10,
the inorganic fine particles have a number average primary particle diameter of 10nm to 300 nm.
14. The electrophotographic photoreceptor according to claim 10,
the inorganic fine particles are composed of at least 1 of tin oxide and titanium oxide.
15. The electrophotographic photoreceptor according to claim 10,
the inorganic fine particles are composite fine particles in which a metal oxide is attached to the surface of a core material as a covering material.
16. The electrophotographic photoreceptor according to claim 15,
in the composite fine particles, the core material is composed of at least 1 of alumina, barium sulfate, and silica.
17. The electrophotographic photoreceptor according to claim 15,
in the composite fine particles, the covering material is composed of at least 1 of tin oxide and titanium oxide.
18. The electrophotographic photoreceptor according to claim 10,
the radical polymerizable functional group is an acryloyl group or a methacryloyl group.
19. A method for manufacturing an electrophotographic photoreceptor, which comprises forming a photosensitive layer on a conductive support and forming a surface layer on the photosensitive layer,
the method comprises a step of applying a coating liquid for surface layer formation containing a compound having two or more radical polymerizable functional groups, inorganic fine particles at least a part of the surface of which is formed of a metal oxide, and organic resin fine particles, which are surface-treated with a coupling agent and are composed of a resin containing at least one constituent unit derived from melamine and benzoguanamine, on a photosensitive layer to form a coating film, and curing the coating film.
20. An image forming apparatus is characterized by comprising:
an electrophotographic photoreceptor, a charging mechanism for charging the surface of the electrophotographic photoreceptor, an exposure mechanism for forming an electrostatic latent image on the surface of the electrophotographic photoreceptor, a developing mechanism for developing the electrostatic latent image with a developer containing a toner to form a toner image, a transfer mechanism for transferring the toner image to a transfer material, a fixing mechanism for fixing the toner image transferred to the transfer material, and a cleaning mechanism for removing residual toner on the electrophotographic photoreceptor,
the cleaning mechanism is composed of a scraper blade,
the electrophotographic photoreceptor described in any one of claims 10 to 18.
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